Product study of the reaction of OH radicals with isoprene in the atmosphere simulation chamber SAPHIR

Atmospheric oxidation of isoprene and its oxidation products methacrolein (MACR) and methyl vinyl ketone (MVK) have an important impact on the photochemical activity in the boundary layer, in particular in forested areas. The oxidation of isoprene by OH radicals was investigated in chamber experiments conducted under tropospheric conditions in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. The aim was to determine the product yield of MVK and MACR in the OH-induced isoprene oxidation and the rate constant of their reaction with OH under real atmospheric conditions. The recently published updated degradation scheme for isoprene from Geiger et al. (2003) was used to determine rate constants and product yields. The fractional yields in the isoprene peroxy radical reaction with NO were found to be 0.41±0.03 for MVK and 0.27±0.03 for MACR. The rate coefficient for MACR with OH was found to be in very good agreement with the recommended value of IUPAC Atkinson (Atkinson et al., 2005). while the rate coefficient for MVK with OH was 27% lower.     

Further studies of the temperature dependence of the rate coefficients for the reactions of OH with a series of ethers under simulated atmospheric conditions

The following temperature-dependent rate coefficients (k/cm³ molecule^–1 s^–1) of the reactions of hydroxyl radicals with aliphatic ethers have been determined over the temperature range 247–373 K by a competitive flow technique: diethyl ether,k _OH=5.2×10^–12 exp[(262±150)/T]; methyln-butyl ether,k _OH=5.4×10^–12 exp[(309±150)/T]; ethyln-butyl ether,k _OH=7.3×10^–12 exp[(335±150)/T]; di-n-butyl ether,k _OH=5.5×10^–12 exp[(502±150)/T] and di-n-pentyl ether,k _OH=8.5×10^–12 exp[(417±150)/T]. The data have been measured relative to the rate coefficientk(OH + 2,3-dimethylbutane)=6.2×10^–12 cm³ molecule^–1 s^–1 independent of temperature.Previous discrepancies in the room-temperature rate coefficients for the OH reactions with ethyln-butyl ether and di-n-butyl ether, obtained in the flow and static experiments of Bennett and Kerr (J. Atmos. Chem. 8, 87–94, 1989;10, 29–38, 1990) compared with those of Wallingtonet al. (Int. J. Chem. Kinet. 20, 541–547, 1988;21, 993–1001, 1989) and of Nelsonet al. (Int. J. Chem. Kinet. 22, 1111–1126, 1990) have been resolved. The results are considered in relation to the available literature data and evaluated rate expressions are deduced where possible. The data are also discussed in terms of structure-activity relationships.     

A Study of the Reaction of OH Radicals with N-Methyl Pyrrolidinone,N-Methyl Succinimide and N-Formyl Pyrrolidinone

A study of the oxidation mechanism of N-methyl pyrrolidinone (C₅H₉NO, NMP) initiated by hydroxyl radicals was made at EUPHORE at atmospheric pressure (1000 ± 10) mbar of air and ambient temperature (T = 300 ± 5 K). The main products were N-methyl succinimide (NMS) (52 ± 4)% and N-formyl pyrrolidinone (FP) (23 ± 9)%. The relative rate technique was used to determine the rate constants of OH with NMP, NMS and FP, the measured values were (in units of cm³ molecule ^{− 1} s^{− 1}): k_NMP = (2.2 ± 0.4) × 10^{− 11}, k_NMS = (1.4 ± 0.3) × 10^{− 12} and k_FP = (6 ± 1) × 10^{− 12}. The results are presented and discussed in terms of the atmospheric impact.     

Latitudinal variation of measured O3 photolysis frequencies J(O1D) and primary OH production rates over the Atlantic Ocean between 50° N and 30° S

The latitudinal variation of the photolysis frequency of ozone to O(¹D) atoms, J(O¹D), was measured using a filter radiometer during the cruise ANT VII/1 of the research vessel Polarstern in September/October 1988. The J(O¹D) noon values exhibited a maximum of 3.6×10^-5 s^-1 (2 sr) at the equator and decreased strongly towards higher latitudes. J(O¹D) reached highest values for clean marine background air with low aerosol load and almost cloudless sky. The J(O¹D) data, measured under these conditions and a temperature of 295 K, can be expressed by: % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOsaiaacI% cacaqGpbWaaWbaaSqabeaaiiaacqWF8baFaaGccaqGebGaaeykaiaa% bccacqWF9aqpcaqGGaGaaeyzaiaabIhacaqGWbGaaeiiaiaabUhacq% GHsislcaaI4aGaaiOlaiaaicdacaaIYaGaeyOeI0IaaGioaiaac6ca% caaI4aGaaiiEaiaaigdacaaIWaWaaWbaaSqabeaacqGHsislcaaIZa% aaaOGaaeiiaiaabIhacaqGGaGaam4uaiabgUcaRiaaiodacaGGUaGa% aGinaiaacIhacaaIXaGaaGimamaaCaaaleqabaGaeyOeI0IaaGOnaa% aakiaadofadaahaaWcbeqaaiaaikdaaaGccaGG9bGaaeikaiaaboha% daahaaWcbeqaaiabgkHiTiaaigdaaaGccaGGPaaaaa!5EE9!\[J({\text{O}}^| {\text{D) }} = {\text{ exp \{ }} - 8.02 - 8.8x10^{ - 3} {\text{ x }}S + 3.4x10^{ - 6} S^2 \} {\text{(s}}^{ - 1} )\] where S represents the product of the overhead ozone column (DU) and the secant of the solar zenith angle. The meridional profile of the primary OH radical production rate P(OH) was calculated from the J(O¹D) measurements and simultaneously recorded O₃ and H₂O mixing ratios. While the latitudinal distribution of J(O¹D) and water vapour was nearly symmetric to the equator, high tropospheric ozone levels up to 40 ppb were observed in the Southern Hemisphere, SH, resulting in higher P(OH) in the SH.     

Impact of Non-Methane Hydrocarbons on Tropospheric Chemistry and the Oxidizing Power of the Global Troposphere: 3-Dimensional Modelling Results

The impact of natural and anthropogenicnon-methane hydrocarbons (NMHC) on troposphericchemistry is investigated with the global,three-dimensional chemistry-transport model MOGUNTIA.This meteorologically simplified model allows theinclusion of a rather detailed scheme to describeNMHC oxidation chemistry. Comparing model resultscalculated with and without NMHC oxidation chemistryindicates that NMHC oxidation adds 40–60% to surfacecarbon monoxide (CO) levels over the continents andslightly less over the oceans. Free tropospheric COlevels increase by 30–60%. The overall yield of COfrom the NMHC mixture considered is calculated to beabout 0.4 CO per C atom. Organic nitrate formationduring NMHC oxidation, and their transport anddecomposition affect the global distribution of NO _x and thereby O₃ production. The impact of theshort-lived NMHC extends over the entire tropospheredue to the formation of longer-lived intermediateslike CO, and various carbonyl and carboxyl compounds.NMHC oxidation almost doubles the net photochemicalproduction of O₃ in the troposphere and leads to20–80% higher O₃ concentration inNO _x -rich boundarylayers, with highest increases over and downwind ofthe industrial and biomass burning regions. Anincrease by 20–30% is calculated for the remotemarine atmosphere. At higher altitudes, smaller, butstill significant increases, in O₃ concentrationsbetween 10 and 60% are calculated, maximizing in thetropics. NO from lightning also enhances the netchemical production of O₃ by about 30%, leading to asimilar increase in the global mean OH radicalconcentration. NMHC oxidation decreases the OH radicalconcentrations in the continental boundary layer withlarge NMHC emissions by up to 20–60%. In the marineboundary layer (MBL) OH levels can increase in someregions by 10–20% depending on season and NO _x levels.However, in most of the MBL OH will decrease by10–20% due to the increase in CO levels by NMHCoxidation chemistry. The large decreases especiallyover the continents strongly reduce the markedcontrasts in OHconcentrations between land and oceanwhich are calculated when only the backgroundchemistry is considered. In the middle troposphere, OHconcentrations are reduced by about 15%, although dueto the growth in CO. The overall effect of thesechanges on the tropospheric lifetime of CH₄ is a 15%increase from 6.5 to 7.4 years. Biogenic hydrocarbonsdominate the impact of NMHC on global troposphericchemistry. Convection of hydrocarbon oxidationproducts: hydrogen peroxides and carbonyl compounds,especially acetone, is the main source of HO _x in theupper troposphere. Convective transport and additionof NO from lightning are important for the O₃ budgetin the free troposphere.     

DMS and SO2 at Baring Head, New Zealand: Implications for the Yield of SO2 from DMS

Atmospheric dimethyl sulfide (DMS) and sulfur dioxide (SO₂) concentrations were measured at Baring Head, New Zealandduring February and March 2000. Anti-correlated DMS and SO₂ diurnalcycles, consistent with the photochemical production of SO₂ from DMS, were observed in clean southerly air off the ocean. The data is used to infer a yield of SO₂ from DMS oxidation. The estimated yields are highly dependent on assumptions about the DMS oxidation rate. Fitting the measured data in a photochemical box model using model-generated OH levels and the Hynes et al. (1986) DMS + OH rate constant suggests that theSO₂ yield is 50–100%, similar to current estimates for the tropical Pacific.However, the observed amplitude of the DMS diurnal cycle suggests that the oxidation rate is higher than that used by the model, and therefore, that theSO₂ yield is lower in the range of 20–40%.     

An Alternative Approach for CO2 Flux Correction Caused by Heat and Water Vapour Transfer

Energy and CO₂ fluxes are commonly measured above plant canopies using an eddy covariance system that consists of a three-dimensional sonic anemometer and an H₂O/CO₂ infrared gas analyzer. By assuming that the dry air is conserved and inducing mean vertical velocity, Webb et al. (Quart. J. Roy. Meteorol. Soc. 106, 85-100, 1980) obtained two equations to account for density effects due to heat and water vapour transfer on H₂O/CO₂ fluxes. In this paper, directly starting with physical consideration of air-parcel expansion/compression, we derive two alternative equations to correct for these effects that do not require the assumption that dry air is conserved and the use of the mean vertical velocity. We then applied these equations to eddy flux observations from a black spruce forest in interior Alaska during the summer of 2002. In this ecosystem, the equations developed here led to increased estimates of CO₂ uptake by the vegetation during the day (up to about 20%), and decreased estimates of CO₂ respiration by the ecosystem during the night (approximately 4%) as compared with estimates obtained using the Webb et al. approach.     

Structure-Reactivity Based Estimation of the Rate Constants for Hydroxyl Radical Reactions with Hydrocarbons

The reaction with the OH radical constitutes the singlemost important removal process for most organiccompounds found in the atmosphere. Efforts to measurethe OH radical rate constants of all troposphericconstituents remain incomplete due to the largevariety of primary emitted compounds and theirtropospheric degradation products.Based on the measured rate constants of 250molecules with the OH radical, a structure-activityrelationship (SAR) for OH reactions has beendeveloped. The molecules used in the dataset includemost classes of tropospheric compounds (includingalkanes, alkenes, and oxygenated hydrocarbons), withthe exception of aromatic and halogen-containingcompounds. Using a new parameterization of themolecular structure, the overall agreement betweenmeasured values and those estimated using the SARdeveloped in this study is usually very good, with10% of the molecules showing deviations larger than50%. In particular, the estimated rate constants ofethers and ketones are in better agreement withexperimental data than with previous SARs (Kwok andAtkinson, Atmos. Environ. 29, 1685–1695,1995). Rate constants of organic nitrates werenot well described by the SAR used in thisstudy. The basic assumption that the additive rateconstant for a chemical group is only influenced byneighbouring functional groups did not allow a goodparameterization for the rate constants of organicnitrates. The use of a second parameter to alter thereactivity of C-H bonds in -position to thefunctional group resulted in markedly better agreementbetween calculated and measured rate constants, butwas not extended due to the limited set of data. This indicates that strong electron withdrawing groups(e.g., nitrate groups) might influence the reactivityof C-H bonds that are not directly adjacent.     

Measurements of tropospheric OH concentrations: A comparison of field data with model predictions

Using long path UV absorption spectroscopy we have measured OH concentrations close to the earth's surface. The OH values observed at two locations in Germany during 1980 through 1983 range from 0.7×10⁶ to 3.2×10⁶ cm^-3. Simultaneously we measured the concentrations of O₃, H₂O, NO, NO₂, CH₄, CO, and the light non methane hydrocarbons. We also determined the photolysis rates of O₃ and NO₂. This allows calculations of OH using a zero dimensional time depdendent model. The modelled OH concentrations significantly exceed the measured values for low NO _x concentrations. It is argued that additional, so far unidentified. HO _x loss reactions must be responsible for that discrepancy.     

Coping with climate variability and climate change in La Ceiba,Honduras

La Ceiba, Honduras, a city of about 200,000 people, lies along the Caribbean Sea, nestled against a mountain range and the Rio Cangrejal. The city faces three flooding risks: routine flooding of city streets due to the lack of a stormwater drainage system; occasional major flooding of the Rio Cangrejal, which flows through the city; and flooding from heavy rainfall events and storm surges associated with tropical cyclones. In this study, we applied a method developed for the U.S. Agency for International Development and then worked with stakeholders in La Ceiba to understand climate change risks and evaluate adaptation alternatives. We estimated the impacts of climate change on the current flooding risks and on efforts to mitigate the flooding problems. The climate change scenarios, which addressed sea level rise and flooding, were based on the Intergovernmental Panel on Climate Change estimates of sea level rise (Houghton et al. 2001) and published literature linking changes in temperature to more intense precipitation (Trenberth et al., Bull Am Meteorol Soc, 84:1205–1217, 2003) and hurricanes (Knutson and Tuleya, J Clim, 17:3477–3495, 2004). Using information from Trenberth et al., Bull Am Meteorol Soc, 84:1205–1217, (2003) and Knutson and Tuleya, J Clim, 17:3477–3495, 2004, we scaled intense precipitation and hurricane wind speed based on projected temperature increases. We estimated the volume of precipitation in intense events to increase by 2 to 4% in 2025 and by 6 to 14% by 2050. A 13% increase in intense precipitation, the high scenario for 2050, could increase peak 5-year flood flows by about 60%. Building an enhanced urban drainage system that could cope with the estimated increased flooding would cost one-third more than building a system to handle current climate conditions, but would avoid costlier reconstruction in the future. The flow of the Rio Cangrejal would increase by one-third from more intense hurricanes. The costs of raising levees to protect the population from increased risks from climate change would be about $1 million. The coast west of downtown La Ceiba is the most vulnerable to sea level rise and storm surges. It is relatively undeveloped, but is projected to have rapid development. Setbacks on coastal construction in that area may limit risks. The downtown coastline is also at risk and may need to be protected with groins and sand pumping. Stakeholders in La Ceiba concluded that addressing problems of urban drainage should be a top priority. They emphasized improved management of the Rio Cangrejal watershed and improved storm warnings to cope with risks from extreme precipitation and cyclones. Adoption of risk management principles and effective land use management could also help reduce risks from current climate and climate change.     

Kinetics of the reactions of hydroxyl radicals with aliphatic ethers studied under simulated atmospheric conditions

Rate coefficients have been measured for the reactions of hydroxyl radicals with a range of aliphatic ethers by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, isobutene and an ether were photolyzed in a Teflon-bag smog chamber. From the rates of depletion of the ether and of the isobutene, and based on the value of the rate coefficient k(OH+i-C₄H₈)=5.26×10^-11 cm³ molecule^-1 s^-1, the following rate coefficients were obtained for the hydroxyl radical reactions at 750 Torr and at 294±2K in units of 10^-12 cm³ molecule^-1 s^-1: diethylether = 12.0±1.1, di-n-propylether = 15.3±1.6, di-n-butylether=17.1±0.9, ethyl n-butylether = 13.5±0.4, ethyl t-butyl-ether = 5.6±0.5, and di-isobutylether = 26.1±1.6. The quoted error limits correspond to 2 standard deviations but do not include any contribution from k(OH+i-C₄H₈) for which the error limits are estimated to be about ±10%. The results are discussed in relation to the available literature data and considered in terms of the structure-activity relation for hydroxyl radical reactions with organic molecules.     

Kinetics of the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds studied under simulated atmospheric conditions

Rate constants have been measured for the reactions of hydroxyl radicals with alkyl nitrates and with some oxygen-containing organic compounds by a competitive technique. Mixtures of synthetic air containing a few ppm of nitrous acid, ethylene and the organic substrate were photolysed in a Teflon bag smog chamber. Based on the value k _HO+C2H₄}=8.1×10^-12 cm³ molecule^-1 s^-1 the following rate constants were obtained for the hydroxyl radical reactions at 750 Torr and at 303 K in units of 10^-12 cm³ molecule^-1: CH₃ONO₂, 0.37±0.09; C₂H₅ONO₂, 0.48±0.20; n-C₃H₇ONO₂, 0.70±0.22; C₂H₅OH, 3.6±0.4; CH₃COCH₃, 0.26±0.08; CH₃CO₂ i-C₃H₇, 3.0±0.8; CH₃CO₂ n-C₃H₇, 2.4±0.2. The results are discussed in relation to the available literature data and the implications of the results are considered in terms of the smog reactivity of these molecules.     

The NO2 absorption spectrum. II. Absorption cross-sections at low temperatures in the 400–500 nm region

With improved experimental conditions already used for measurements at ambient temperature (Mérienneet al., 1994), new values have been found for the absorption cross-sections of NO₂ at 240 and 220 K in the 400–500 nm spectral region. Using a better resolution than in previous studies we show that the temperature effect is not negligible and should be taken into account for the optical measurements of atmospheric NO₂ amounts by differential absorption methods.Unité de Recherche Associée au CNRS.     

Distribution of n-alkanes and PAHs in atmospheric aerosols

The concentrations of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) are determined in atmospheric aerosol samples collected at a rural sampling site in Hungary. For the n-alkanes the chromatographic profiles are established and the average carbon number and carbon preference index (CPI) are calculated. An attempt is made to obtain the origin of n-alkanes found in atmospheric aerosol samples. Based on the results of the measurements the probable importance of a round-the-year biogenic source for the n-alkanes with CPIs close to unity is emphasized.     

Incorporation of Non-Linear Effective Cross-Section Parameterizations into a Fast Photolysis Computation Code (Fast-J)

We have investigated several methods of incorporating laboratorymeasurements of effective cross-sections (quantum yield timesabsorption cross-section) that are non-linear functions oftemperature, pressure, and wavelength, into the Fast-J photolysis codeof Wild et al. (2000). The best method was found to beparameterization of the solar weighted effective cross-section usingthe form of the effective cross-section, with numerical fitting of theparameterization constants. Using this technique on the acetone dataof Gierczak et al. (1998) produces aparameterization which fits all points to within 1%. This methodshould also benefit other photolysis codes with large wavelength bins.     

GHOST – A Novel Airborne Gas Chromatograph for In Situ Measurements of Long-Lived Tracers in the Lower Stratosphere: Method and Applications

A novel fully-automated airborne gas chromatograph for in situmeasurements of long-lived stratospheric tracers hasbeen developed, combining the high selectivity of a megabore PLOTcapillary column with recently developed sampling and separationtechniques. The Gas cHromatograph for theObservation of Stratospheric Tracers (GHOST)has been successfully operated during three STREAM campaigns(Stratosphere TRoposphere Experiment byAirborne Measurement) onboard a Cessna Citation IIaircraft in two different modes: Either N₂O andCF₂Cl₂(CFC-12) or CFC-12 and CFCl₃ (CFC-11) have been measuredsimultaneously, with a time resolution of 2 min for both modes.Under flight conditions the instrument precision (1) forthese species is better than 0.9%, and the accuracy(1) is better than 2.0% of the tropospheric values ofall measured compounds. The detection limits (3) arebelow 28 ppb for N₂O, 14 ppt for CFC-12, and 8 ppt forCFC-11, respectively, i.e., well below 10 % of the troposphericvalues of all measured compounds. Post-mission optimization of thechromatographic separation showed a possible enhancement of thetime resolution by up to a factor of 2, associated with acomparable increase in precision and detection limit. As test ofactual performance of GHOST results from an in-flight N₂Ointercomparison with a tunable diode laser absorptionspectrometer (TDLAS) are presented. They yield an excellentagreement between both instruments. Furthermore, on the basis ofthe hitherto most extensive set of upper tropospheric and lowerstratospheric data, the relative stratospheric N₂2O lifetime isre-assessed. When referenced to the WMO reference CFC-11 lifetimeof 45 ± 7 years an N₂O lifetime of 91 ± 15 yearsis derived, a value substantially smaller than the WMO referencelifetime of 120 years. Moreover, this value implies astratospheric N₂O sink strength of 16.3 ± 2.7 Tg (N)yr^–1 which is 30% larger than previous estimates.     

The NO2 Absorption Spectrum. IV: The 200–400 nm Region at 220 K

Previous experiments in the 400–500 nm region (Coquart et al., 1995) have been extended to the 200–400 nm region to determine the absorption cross-sections of NO₂ at 220 K. The NO₂ and N₂O₄ cross-sections are obtained simultaneously from a calculation applied to the data resulting from measurements at low pressures. A comparison between the NO₂ cross-sections at 220 K and at ambient temperature shows that the low temperature cross-sections are generally lower, except in the region of the absorption peaks. Comparisons are also made with previous data at temperature close to 220 K.     

On the Budget of OH Radicals and Ozone in an Urban Plume from the Decay of C5–C8 Hydrocarbons and NOx

Simultaneous measurements of ozone and ozoneprecursors were made during a field campaign atSchauinsland in the Black Forest and in the valleynorth of Schauinsland that channels the flow ofpolluted air from the city of Freiburg to the site.From the decay of hydrocarbons and NO_x between the twomeasuring sites and the known rate coefficients, theconcentration of OH radicals was calculated. From abudget analysis of OH and HO_x it is concluded that therelatively high OH concentrations (5–8 ×10⁶cm^-3) in the presence of high NO₂concentrations cannot be explained by the knownprimary sources. The budget can be closed if efficientrecycling of OH via HO₂ is assumed to occur andthat, based on the measured hydrocarbons, 2 HO₂molecules are formed for each OH radical that reactswith a hydrocarbon molecule. This assumption is inaccordance with the budget of O_x obtained from ourmeasurements and with results from earliermeasurements of alkylnitrates and peroxy radicals atSchauinsland. A possible conclusion is that the decayof precursors and production of photooxidants in urbanplumes proceeds at a faster rate than is currentlyassumed. The potential role of biogenichydrocarbons for the radical budget is alsodiscussed.     

Laboratory Kinetic Studies of the Reactions of Cl Atoms with Species of Biogenic Origin: δ3-Carene, Isoprene, Methacrolein and Methyl Vinyl Ketone

The rate coefficients for the reaction between atomic chlorine and a number of naturally occurring species have been measured at ambient temperature and atmospheric pressure using the relative rate technique. The values obtained were (4.0 ± 0.8) × 10^-10, (2.1 ± 0.5) × 10^-10, (3.2 ± 0.5) × 10^-10, and (4.9 ± 0.5) × 10^-10 cm³ molecule^-1 s^-1, for reactions with isoprene, methyl vinyl ketone, methacrolein and ³-carene, respectively. The value obtained for isoprene compares favourably with previously reported values. No values have been reported to date for the rate constants of the other reactions.     

Cape Grim isotope measurements — A preliminary assessment

Measurements of the stable carbon isotope ratio in atmospheric CO₂ permit a distinction between variations resulting from biospheric and oceanic exchange. In situ extraction of CO₂ from Cape Grim air (41°S) for isotopic analysis commenced in 1977; however difficulties with technique reliability were experienced until 1982. Since 1982, 2.6 years of relatively consistent values have accumulated.For a preliminary assessment of the latter data, estimates of the isotopic behaviour from the global transport and inter-reservoir exchange model of Pearman and Hyson (1985) have been employed. The assessment demonstrates the precision requirements of a carbon isotope monitoring program and the relevance of the isotope measurements as a constraint on parameterization of the model.Clear evidence of the changes due to fossil fuel combustion is seen in the year-to-year differences in ¹³C, with the mean and standard error of the overall trend being –0.025±0.005 yr^-1. A significant seasonal variation in ¹³C is apparent, despite considerable inter-annual variability possibly associated with the 1982/83 ENSO phenomena. The average peak-to-peak amplitude is 0.055±0.014 with a maximum on day 85±15 (approx. 26 March).There is some evidence for a complex seasonal inter-relationship between concentration and isotope ratio, both in the Cape Grim data and in Mook et al. (1983) South Pole data, but with marked differences between the stations, and with both different from the model estimates.In particular, the Cape Grim results suggest that exchange with Southern Hemisphere biosphere is the main contributor to the seasonal variation in isotope ratio at this latitude.