A Case Study of Carbon Pools Under Three Different Land-Uses in Panamá

This paper examines changes in carbon (C) pools associated with land-use, synthesizing data from two experiments dealing with different aspects of tree plantation establishment in Central Panamá. First, we analysed soil profiles in a grazed pasture and an adjacent 5-year-old teak (Tectona grandis) plantation. There were small differences in soil C mass in the top 10 cm of the pasture and the plantation, though analysis of paired profiles suggested larger differences at greater depth. Analysis of the ¹³C signatures in the pasture soils and litter showed that 90% to 95% of the organic matter in the surface 5 cm was derived from C₄ pasture plants, over the 45 years since the pasture was converted from forest. Comparison of the ¹³C signatures in the pasture and teak plantation profiles indicated substantial replacement of C₄—derived organic matter with the dominantly C₃—derived plantation tissues. Organic matter turnover times in the upper 10 cm of the soils ranged from 8 to 34 years and from 11 to 58 years in the upper 30 cm, depending on topographic location. We also present preliminary results, and technical challenges, for an eddy covariance experiment set up to provide a direct comparison between a grazed pasture and a native tree plantation. The two ecosystems studied are estimated to be small CO₂ sinks, 92 g,C,m^–2 yr^–1 for the pasture, and 57 g,C,m^–2 yr^–1 for native species plantation in the first year after establishment. The pastures response to seasonal change was more pronounced, both in term of CO₂ fluxes and in term of herbaceous productivity, than the plantations response. The storage below ground systems contained up 40% of the total sapling biomass.     

Mass transfer at the air/water interface: Mass accommodation coefficients of SO2, HNO3, NO2 and NH3

We present here experimental determinations of mass accommodation coefficients using a low pressure tube reactor in which monodispersed droplets, generated by a vibrating orifice, are brought into contact with known amounts of trace gases. The uptake of the gases and the accommodation coefficient are determined by chemical analysis of the aqueous phase.We report in this article measurements of _exp=(6.0±0.8)×10^–2 at 298 K and with a total pressure of 38 Torr for SO₂, (5.0±1.0)×10^–2 at 297 K and total pressure of 52 Torr for HNO₃, (1.5±0.6)×10^–3 at 298 K and total pressure of 50 Torr for NO₂, (2.4±1.0)×10^–2 at 290 K and total pressure of 70 Torr for NH₃.These values are corrected for mass transport limitations in the gas phase leading to =(1.3±0.1)×10^–1 (298 K) for SO₂, (1.1±0.1)×10^–1 (298 K) for HNO₃, (9.7±0.9)×10^–2 (290 K) for NH₃, (1.5±0.8)×10^–3 (298 K) for NO₂ but this last value should not be considered as the true value of for NO₂ because of possible chemical interferences.Results are discussed in terms of experimental conditions which determine the presence of limitations on the mass transport rates of gaseous species into an aqueous phase, which permits the correction of the experimental values.     

On Modeling Dry Deposition of Long-Lived and Chemically Reactive Species over Heterogeneous Terrain

An explicit multi-layer subgrid-scheme was developed for ameso-/-scale model to consider subgrid-scale surface heterogeneity, dry deposition, biogenic and anthropogenic emission of trace gases. Since dry deposition measurements of highly reactive trace species are scarce we try to evaluate this scheme by heuristic principles. The results of simulations conducted for a 5×5 km² resolution with and without thisscheme are evaluated by using results of a model run with 1×1 km²resolution, which is taken as a `grand thruth' and which has the same resolution as the subgrid. The explict multi-layer subgrid scheme provides a similar distribution of dry deposition fluxes as the much more computationally expensive simulation with the 1×1 km² resolution.Dry deposition fluxes determined from observations give evidence that the explicit multi-layer subgrid scheme which does not require a constant flux approximation for a layer of several decameters leads to an improvement in determining the exchange between the atmosphere and the ground.Results of simulations with a microscale model show that the inhomogeneity at forest edges leads to an increase of the turbulent transports of up to a factor 4 compared to horizontally homogeneous terrain, which is assumed to be the conditions of the subgrid cells (and which is usually the assumption for the entire grid cell in mesoscale models). Inhomogeneity inside an extended stand of trees causes an overall increase of 5–10% withhigh local extremes, i.e. such an inhomogeneity results to an underestimation of dry deposition in meso-/-scale models. The effects are most pronounced for a wind direction perpendicular to the forest edge.     

Landscape-Scale Analysis of Interactions between Insect Defoliation and Forest Fire in Central Canada

Analysis of Ontario's historical records from 1941–1996 showed that spruce budworm, Choristoneura fumiferana (Clem.) caused whole tree mortality within 389×10³ km². This amounted to 9.2% of the annually cumulative area with moderate-severe defoliation. Large (>2 km²) fires were reported in approximately 65,000 km² and overlapped only 2.8% of the area of reported spruce budworm (SBW) caused tree mortality. Within the 417×10³ km² defoliated by SBW at least once in 1941–1996, the maximum total area recorded as defoliated in any year was over 20 times the maximal area burnt. In the 19,950 km² experiencing both wildfire and SBW defoliation, analysis of the spectra of time lags between the two disturbance types indicated that fires occurred 3–9 years after a SBW outbreak disproportionately often. This window of opportunity for wildfire varies geographically: it starts later after SBW outbreak and lasts longer in western than in eastern Ontario. In addition, 7.5% of the areas containing SBW killed trees were burnt in western compared to 4.8% in eastern Ontario. These geographical differences may result at least partly from slower decomposition of dead fuels in the drier climates of the western SBW belt compared to the eastern SBW belt. The implications for climatic change are discussed.     

Trace gas measurements at the monitoring station cape point,South Africa,between 1978 and 1988

Since 1978, a measuring station has been operated at Cape Point (34°21 S, 18°29 E). In this article, results of measurements of CO, CFCl₃, CCl₄, O₃, N₂O and CH₄ are presented as monthly means and analyzed with respect to long-term trends and seasonal variations. For CO and CH₄, very similar seasonal variations have been observed, indicating strong interrelations between these two gases. For CO and O₃, no significant changes of the mean annual concentrations can be established for the observation periods of 10 and 5 years, respectively. The measurements yield a growth rate of 9.1 pptv yr^-1 for CFCl₃ (1980–1987) and 0.6 ppbv yr^-1 for N₂O (1983–1987). The concentration increases of CH₄ (10.3 ppbv yr^-1 for 1983–1987) and of CCl₄ (2.1 pptv yr^-1 for 1980–1988) are analyzed for temporal changes during the last years.Presented at the Second Conference on Baseline Observations in Atmospheric Chemistry (SABOAC II) in Melbourne, Australia, November 1988.     

Airborne measurements of savanna fire emissions and the regional distributio of pyrogenic pollutants over Western Africa

We measured CO₂, CO, CH₄, H₂, and NO₂ in air masses polluted by savanna fires over Côte d'Ivoire, western Africa. Elevated concentrations of these trace gases were found in fire plumes and also in extensive haze layers. Trace gas mixing ratios ranged as high as 605 ppmv for CO₂, 14.8 ppmv for CO, 2.7 ppmv for CH₄, 4.2 ppmv for H₂, and 25 ppbv for NO₂. We compare our emission ratios to those obtained in previous field and laboratory studies. The emission ratios, expressed as an average and as a range or as an average only, were: dCO/dCO₂ 5.3×10^–2 (3–18×10^–2); dCH₄/dCO 5.3×10^–2; dH₂/dCO 2.4×10^–1 and dNO₂/dCO₂ 1.8×10^–4 (1.5–2.2×10^–4). The values found match those found during similar measurements, though our results point to rather vigorous burning in the savanna of western Africa.     

Carbonyl sulfide emissions from biomass burning in the tropics

Carbonyl sulfide emissions from biomass burning have been studied during field experiments conducted both in an African savanna area (Ivory Coast) and rice fields, central highland pine forest and savanna areas in Viet-Nam. During these experiments CO₂, CO and C₂H₂ or CH₄ have also been also monitored. COS values range from 0.6 ppbv outside the fires to 73 ppbv in the plumes. Significant correlations have been observed between concentrations of COS and CO (R ²=0.92,n=25) and COS and C₂H₂ (R ²=0.79,n=26) indicating a COS production during the smoldering combustion. COS/CO₂ emission factors (COS/CO₂) during field experiments ranged from 1.2 to 61×10^–6 (11.4×10^–6 mean value). COS emission by biomass burning was estimated to be up to 0.05 Tg S/yr in tropics and up to 0.07 Tg S/yr on a global basis, contributing thus about 10% to the global COS flux. Based on the S/C ratio measured in the dry plant biomass and the COS/CO₂ emission factor, COS can account for only about 7% of the sulfur emitted in the atmosphere by biomass burning.     

Influence of Transport over a Mountain Ridge on the Chemical Composition of Marine Aerosols during the ACE-2 Hillcloud Experiment

Aerosol chemical composition and trace gas measurements were made at twolocations on the northeastern peninsula of Tenerife during the ACE-2HILLCLOUD experiment, between 28 June and 23 July 1997. Measurementswere made of coarse (#gt;2.5 m aerodynamic diameter) and fine (#lt; 2.5m) aerosol Cl^–, NO₃ ^–,SO₄ ^2–, non-sea saltSO₄ ^2– (NSSS),CH₃SO₃ ^– (MSA) andNH₄ ⁺, and gas phase dimethylsulphide (DMS), HCl,HNO₃, SO₂, CH₃COOH, HCOOH andNH₃. Size distributions were measured using a cascadeimpactor. Results show that in marine air masses NSSS and MSA wereformed via DMS oxidation, with additional NSSS present in air massescontaining a continental component. Using a Eulerian box model approachfor aerosols transported between upwind and downwind sites, a mean NSSSproduction rate of 4.36 × 10^–4 gm^–3 s^–1 was calculated for daytimeclear sky periods (highest insolation), with values for cloudy periodsduring daytime and nighttime of 3.55 × 10^–4 and2.40 × 10^–4 g m^–3s^–1, respectively. The corresponding rates for MSA were6.23 × 10^–6, 8.49 × 10^–6and 6.95 × 10^–6 g m^–3s^–1, respectively. Molar concentration ratios forMSA/NSSS were 8.7% (1.8–18.2%) and 1.9%(1.3–3.5%) in clean and polluted air masses, respectively.Reactions occurring within clouds appeared to have a greater influenceon rates of MSA production, than of NSSS, while conversely daytime gasphase reactions were more important for NSSS. For MSA, nighttimein-cloud oxidation rates exceeded rates of daytime gas phase productionvia OH oxidation of DMS. NSSS, MSA and ammonium had trimodal sizedistributions, with modes at 0.3, 4.0 and >10.0 m (NSSS andNH₄ ⁺), and 0.3, 1.5 and 4.0 m (MSA). Nosignificant production of other aerosol species was observed, with theexception of ammonium, which was formed at variable rates dependent onneutralisation of the aerosol with ammonia released from spatiallynon-uniform surface sources. Seasalt components were mainly present incoarse particles, although sub-micrometre chloride was also measured.Losses by deposition exceeded calculated expectations for all species,and were highest for the seasalt fraction and nitrate.     

Emission of nitrous oxide from temperate forest soils into the atmosphere

N₂O emission rates were measured during a 13-month period from July 1981 till August 1982 with a frequency of once every two weeks at six different forest sites in the vicinity of Mainz, Germany. The sites were selected on the basis of soil types typical for many of the Central European forest ecosystems. The individual N₂O emission rates showed a high degree of temporal and spatial variabilities which, however, were not significantly correlated to variabilities in soil moisture content or soil temperatures. However, the N₂O emission rates followed a general seasonal trend with relatively high values during spring and fall. These maxima coincided with relatively high soil moisture contents, but may also have been influenced by the leaf fall in autumn. In addition, there was a brief episode of relatively high N₂O emission rates immediately after thawing of the winter snow. The individual N₂O emission rates measured during the whole season ranged between 1 and 92 g N₂O-N m^–2 h^–1. The average values were in the range of 3–11 g N₂O-N m^–2 h^–1 and those with a 50% probability were in the range of 2–8 g N₂O-N m^–2 h^–1. The total source strength of temperate forest soils for atmospheric N₂O may be in the range of 0.7–1.5 Tg N yr^–1.     

FT-IR Study of the Kinetics and Products of the Reactions of Dimethylsulphide, Dimethylsulphoxide and Dimethylsulphone with Br and BrO

Kinetics and products of the gas-phase reactions of dimethylsulphide (DMS), dimethylsulphoxide (DMSO) and dimethylsulphone (DMSO₂) with Br atoms and BrO radicals in air have beeninvestigated using on-line Fourier Transform Infrared Spectroscopy (FT-IR) as analytical technique at 740 ± 5 Torr total pressure and at 296 ± 3 K in a480 L reaction chamber. Using a relative rate method for determining the rate constants; the following values (expressed in cm³molecule^–1 s^–1) were found: k_DMS+Br = (4.9 ±1.0) ×10^–14, k_DMSO + Br < 6 × 10^–14,k_{DMSO 2} + Br 1 × 10^–15,k_DMSO + BrO = (1.0 ± 0.3) × 10^–14 andk_{DMSO 2} + BrO 3 × 10^–15 (allvalues are given with one on the experimental data). DMSO, SO₂, COS, CH₃SBr andCH₃SO₂Br were identified as the main sulphur containing products of the oxidation of DMS by Br atoms. From the reaction between DMSO and Br atoms, DMSO₂and CH₃SO₂Br were the only sulphur containing products thatwere identified. DMSO, DMSO₂ and SO₂ were identified as themain sulphur containing products of the reaction between DMS and BrO.DMSO₂ was found to be the only product of the reaction between DMSO and BrO. For the reactions of DMSO₂ with Br and BrO no products were identified because the reactions were too slow.The implications of these results for atmospheric chemistry are discussed.     

Fourier transform infrared studies of the reaction of Cl atoms with PAN,PPN, CH3OOH,HCOOH, CH3COCH3 and CH3COC2H5 at 295±2 K

The relative rate technique has been used to measure rate constants for the reaction of chlorine atoms with peroxyacetylnitrate (PAN), peroxypropionylnitrate (PPN), methylhydroperoxide, formic acid, acetone and butanone. Decay rates of these organic species were measured relative to one or more of the following reference compounds; ethene, ethane, chloroethane, chloromethane, and methane. Using rate constants of 9.29×10^–11, 5.7×10^–11, 8.04×10^–12, 4.9×10^–13, and 1.0×10^–13 cm³ molecule^–1 sec^–1 for the reaction of Cl atoms with ethene, ethane, chloroethane, chloromethane, and methane respectively, the following rate constants were derived, in units of cm³ molecule^–1 s^–1: PAN, <7×10^–15; PPN, (1.14±0.12)×10^–12; HCOOH, (2.00±0.25)×10^–13; CH₃OOH, (5.70±0.23)×10^–11; CH₃COCH₃, (2.37±0.12)×10^–12; and CH₃COC₂H₅, (4.13±0.57)×10^–11. Quoted errors represent 2 and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295±2 K and 700 torr total pressure of nitrogen or synthetic air. The results are discussed with respect to the previous literature data and to the modelling of nonmethane hydrocarbon oxidation in the atmosphere.In recent discussions with Dr. R. A. Cox of Harwell Laboratory, UKAEA, we learnt of a preliminary value for the rate constant of the reaction of Cl with acetone of (2.5±1.0)×10^–12 cm³ molecule^–1 sec^–1 measured by R. A. Cox, M. E. Jenkin, and G. D. Hayman using molecular modulation techniques. This value is in good agreement with our results.     

Comparative measurements and seasonal variations in energy and carbon exchange over forest and pasture in South West Amazonia

Summary Comparative measurements of radiation flux components and turbulent fluxes of energy and CO₂ are made at two sites in South West Amazonia: one in a tropical forest reserve and one in a pasture. The data were collected from February 1999 to September 2002, as part of the Large Scale Biosphere-Atmosphere Experiment in Amazonia (LBA). During the dry seasons, although precipitation and specific humidity are greatly reduced, the soil moisture storage profiles down to 3.4m indicate that the forest vegetation continues to withdraw water from deep layers in the soil. For this reason, seasonal changes observed in the energy partition and CO₂ fluxes in the forest are small, compared to the large reductions in evaporation and photosynthesis observed in the pasture. For the radiation balance, the reflected short wave radiation increases by about 55% when changing from forest to pasture. Combined with an increase of 4.7% in long wave radiation loss, this causes an average reduction of 13.3% in net radiation in the pasture, compared to the forest. In the wet season, the evaporative fraction (E/R_n) at the pasture is 17% lower than at the forest. This difference increases to 24% during the dry season. Daytime CO₂ fluxes are 20–28% lower (in absolute values) in the pasture compared to the forest. The night-time respiration in the pasture is also reduced compared to the forest, with averages 44% and 57% lower in the wet and dry seasons, respectively. As the reduction in the nocturnal respiration is larger than the reduction in the daytime uptake, the combined effect is a 19–67% higher daily uptake of CO₂ in the pasture, compared to the forest. This high uptake of CO₂ in the pasture site is not surprising, since the growth of the vegetation is constantly renewed, as the cattle remove the biomass.     

Rainwater Chemistry and Wet Deposition over the Equatorial Forested Ecosystem of Zoétélé (Cameroon)

Within the framework of IDAF (IGAC DEBITS AFRICA: International GlobalAtmospheric Chemistry/DEposition of Biogeochemically Important TraceSpecies/Africa) network, data analysis is realised on precipitation chemical composition collected in Zoétélé, in Southern Cameroon. This station, located atabout 200 km from the Atlantic Ocean, is representative of a so-called `Evergreen Equatorial Forest' ecosystem. An automatic wet-only precipitation collector was operated at the station from 1996 to 2000. The rainfall regime, associated with eastward advection of moist and cool monsoon air masses, amounts to an average of 1700 mm/year. Inorganic and organic content of the precipitation were determined by IC in 234 rainfall events, representing a total 4,583 mm of rainfall from an overall of 7,100 mm.The mean annual precipitation chemistry and wet deposition fluxes characteristic of an African equatorial forest are quantified. Typical atmospheric gases and particles sources influence the precipitation chemical content and the associated deposition of chemical species. Indeed, hydrogen concentration is the highest (12.0 eq.L^–1) of the IDAF measurements, leading to acid rains with a low mean pH 4.92. The mineral species are dominated by nitrogenous compounds (NH₄ ⁺:10.5 and NO₃ ^–: 6.9 eq.L^–1), Ca²⁺ (8.9 eq.L^–1) and SO₄ ^{2 –} 5.1 eq.L^–1. Relationship between Ca^{2 +} and SO₄ ^{2 –} indicated aterrigeneous particulate source and an additional SO₄ ^{2 –} contributionprobably due to swamps and volcano emissions. Na⁺ and Cl^–concentrations, around 4.0 eq.L^–1, seem very low for this site,accounting for the marine source. Besides, strong correlations between NH₄ ⁺/K⁺/Cl^– indicate the biomass burning originof these species. Accordingly, precipitation chemistry in Zoétéléis influenced by three major sources: biogenic emissions from soil and forest ecosystems, biomass burning from savannah, and terrigenous signature from particles emissions of arid zones; and three minor sources: marine, volcano and anthropogenic. In spite of the relatively low concentration of all these elements, the wet deposition is quite significant due to the high precipitation levels, with for example a nitrogenous compounds deposition of 34 mmol.m^–2.yr^–1.     

Ly(α) absorption cross-section of H2O and O2

The absorption cross-sections of water vapor and oxygen were measured, using a low-pressure radio frequency discharge through traces of hydrogen in argon as a light source for Ly() radiation. The cross-sections are H₂O = 1.59 × 10^–17 cm² and O₂ = 1.13 × 10^–20 + 1.72 × 10^–23 for water and oxygen, respectively, where P is the oxygen pressure in units of Torr. Ly() lamps, such as used for this work, are important light sources for photochemical laboratory work and find applications for trace-gas detection in the atmosphere. For the latter application, accurate cross-sections of water vapor and oxygen are needed.     

Effects of high CO2 levels on surface temperature and atmospheric oxidation state of the early Earth

One-dimensional radiative-convective and photochemical models are used to examine the effects of enhanced CO₂ concentrations on the surface temperature of the early Earth and the composition of the prebiotic atmosphere. Carbon dioxide concentrations of the order of 100–1000 times the present level are required to compensate for an expected solar luminosity decrease of 25–30%, if CO₂ and H₂O were the only greenhouse gases present. The primitive stratosphere was cold and dry, with a maximum H₂O volume mixing ratio of 10^–6. The atmospheric oxidation state was controlled by the balance between volcanic emission of reduced gases, photo-stimulated oxidation of dissolved Fe⁺² in the oceans, escape of hydrogen to space, and rainout of H₂O₂ and H₂CO. At high CO₂ levels, production of hydrogen owing to rainout of H₂O₂ would have kept the H₂ mixing ratio above 2×10^–4 and the ground-level O₂ mixing ratio below 10^–11, even if no other sources of hydrogen were present. Increased solar UV fluxes could have led to small changes in the ground-level mixing ratios of both O₂ and H₂.     

Solubilities of pyruvic acid and the lower (C1-C6) carboxylic acids. Experimental determination of equilibrium vapour pressures above pure aqueous and salt solutions

Henry's law constantsK _H (mol kg^–1 atm^–1) have been determined at 298.15 K for the following organic acids: formic acid (5.53±0.27×10³); acetic acid (5.50±0.29×10³); propionic acid (5.71±0.34×10³);n-butyric acid (4.73±0.18×10³); isobutyric acid (1.13±0.12×10³); isovaleric acid (1.20±0.11×10³) and neovaleric acid (0.353±0.04×10³). They have also been determined fromT=278.15 K toT=308.15 K forn-valeric acid (ln(K _H)=–14.3371+6582.96/T);n-caproic acid (ln(K _H)=–13.9424+6303.73/T) and pyruvic acid (ln(K _H)=–4.41706+5087.92/T). The influence of 9 salts on the solubility of pyruvic acid at 298.15 K has been measured. Pyruvic acid is soluble enough to partition strongly into aqueous atmospheric aerosols. Other acids require around 1 g of liquid water m^–3 (typical of clouds) to partition significantly into the aqueous phase. The degree of partitioning is sensitive to temperature. Considering solubility and dissociation (to formate) alone, the ratio of formic acid to acetic acid in liquid water in the atmosphere (at equilibrium with the gas phase acids) is expected to increase with rising pH, but show little variation with temperature.     

Size-Resolved Characterisation of Soluble Ions in the Particles in the Tropospheric Plume of Masaya Volcano, Nicaragua: Origins and Plume Processing

We present the first application of a multi-stage impactor to study volcanic particle emissions to the troposphere from Masaya volcano, Nicaragua. Concentrations of soluble SO₄ ^2–,Cl^–, F^–, NO₃ ^–, K⁺, Na⁺,NH₄ ⁺, Ca²⁺ and Mg²⁺ were determined in 11 size bins from 0.07 m to >25.5 m. The near-source size distributions showed major modes at 0.5m (SO₄ ^2–, H⁺,NH₄ ⁺); 0.2 m and 5.0 m (Cl^–) and 2.0–5.0 m(F^–). K⁺ and Na⁺ mirrored the SO₄ ^2– size-resolvedconcentrations closely, suggesting that these were transported primarily asK₂SO₄ and Na₂SO₄ in acidic solution, while Mg²⁺ andCa²⁺ presented modes in both <1 m and >1 m particles. Changes in relative humidity were studied by comparing daytime (transparent plume) and night-time (condensed plume) results. Enhanced particle growth rates were observed in the night-time plume as well as preferential scavenging of soluble gases, such as HCl, by condensed water. Neutralisation of the acidic aerosol by background ammonia was observed at the crater rim and to a greater extent approximately 15 km downwind of the active crater. We report measurements of re-suspended near-source volcanic dust, which may form a component of the plume downwind. Elevated levels ofSO₄ ^2–, Cl^–, F^–,H⁺, Na⁺, K⁺ and Mg²⁺ were observed around the 10 m particle diameter in this dust. The volcanic SO₄ ^2– flux leaving the craterwas 0.07 kg s^–1.     

A discharge flow mass-spectrometric study of the reaction between the NO3 radical and isoprene

The kinetics and mechanism of the reactionNO₃+CH₂=C(CH₃)–CH=CH₂productswere studied in two laboratories at 298 K in the pressure range 0.7–3 torr using the discharge-flow mass-spectrometric method. The rate constant obtained under pseudo-first-order conditions with excess of either NO₃ or isoprene was: k ₁=(7.8±0.6)×10^–13 cm³ molecule^–1 s^–1. The product analysis indicated that the primary addition of NO₃ occurred on both -bonds of the isprene molecule.     

Autoxidation of N(III), S(IV), and other Species in Frozen Solution – A Possible Pathway for Enhanced Chemical Transformation in Freezing Systems

The chemistry of glycolaldehyde (hydroxyacetaldehyde) relevant to the troposphere has been investigated using UV absorption spectrometry and FTIR absorption spectrometry in an environmental chamber. Quantitative UV absorption spectra have been obtained for the first time. The UV spectrum peaks at 277 nm with a maximum cross section of (5.5± 0.7)×10^–20 cm² molecule^–1. Studies of the ultraviolet photolysis of glycolaldehyde ( = 285 ± 25 nm) indicated that the overall quantum yield is > 0.5 in one bar of air, with the major products being CH₂OH and HCO radicals. Rate coefficients for the reactions of Cl atoms and OH radicals with glycolaldehyde have been determined to be (7.6± 1.5)×10^–11 and (1.1± 0.3)×10^–11 cm³ molecule^–1 s^–1, respectively, in good agreement with the only previous study. The lifetime of glycolaldehyde in the atmosphere is about 1.0 day for reaction with OH, and > 2.5 days for photolysis, although both wet and dry deposition should also be considered in future modeling studies.     

Degradation of Isoprene in the Presence of Sulphoxy Radical Anions

Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 10⁹ M^–1 s^–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10^–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 10⁸ M^–1 s^–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO^– ₄ adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10^–5 m³ m^–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO₂ in the atmosphere.