Determination of part-per-trillion levels of atmospheric dimethyl sulfide by isotope dilution gas chromatography/mass spectrometry

Stable isotopic dilution was applied to the determination of dimethyl sulfide (DMS) in ambient air at the low part-per-trillion by volume (pptrv) levels. Perdeuterated DMS was used as an internal standard in the gas chromatography/mass spectrometry determination. The isotopically labelled internal standard provided insensitivity to possible losses of DMS in sampling and analysis. The lower limit of detection (LLD) was 1 pptrv with a sample acquisition time of 2 min.     

Grab sampling for the determination of sulfur dioxide and dimethyl sulfide in air by isotope dilution gas chromatography/mass spectrometry

Developments allowing the direct determination of sulfur dioxide and dimethyl sulfide in grab samples by gas chromatography/mass spectrometry with isotopically labeled standards (GC/MS/ILS) are reported. Isotopomers of DMS and SO₂ are used as internal standards. Spiked air samples are dried to a dew point of <–60 °C and trapped cryogenically in loops of Teflon tubing. Sealed samples are transported to the laboratory under liquid nitrogen and later subjected to GC/MS analysis. Holding times of up to one month do not result in significant sample loss. For samples collected in a clean marine environment, concentrations of SO₂ and DMS greater than 5 and 8 pptv, respectively, are significantly different from blanks at the 95% confidence level. Average measurement precision derived from a propagation of errors are 9% for SO₂ and 42% for DMS at concentrations from 5–15 pptv.Improvements are outlined which should provide sensitivity and precision comparable to that of on-site GC/MS. The technique will allow increased flexibility for the determination of trace sulfur species in the field under conditions where deployment of a mass spectrometer is not possible.     

Modelling the equilibrium and transient responses of global temperature to past and future trace gas concentrations

Recent works with energy balance climate models and oceanic general circulation models have assessed the potential role of the world ocean for climatic changes on a decadal to secular time scale. This scientific challenge is illustrated by estimating the response of the global temperature to changes in trace gas concentration from the pre-industrial epoch to the middle of the next century. A simple energetic formulation is given to estimate the effect on global equilibrium temperature of a fixed instantaneous radiative forcing and of a time-dependent radiative forcing. An atmospheric energy balance model couple to a box-advection-diffusion ocean model is then used to estimate the past and future global climalic transient response to trace-gas concentration changes. The time-dependent radiative perturbation is estimated from a revised approximate radiative parameterization, and the recent reference set of trace gas scenarios proposed by Wuebbles et al. (1984) are adopted as standard scenarios. Similar computations for the past and future have recently been undertaken by Wigley (1985), but using a purely diffusive ocean and slightly different trace gas scenarios. The skill of the socalled standard experiment is finally assessed by examining the model sensitivity of different parameters such as the equilibrium surface air temperature change for a doubled CO₂ concentration [T _ae (2×CO₂)], the heat exchange with the deeper ocean and the trace gas scenarios. For T _ae (2×CO₂) between 1 K and 5 K, the following main results are obtained: (i) for a pre-industrial CO₂, concentration of 270 ppmv, the surface air warming between 1850 and 1980 ranges between 0.4 and 1.4 K (if a pre-industrial CO₂ concentration of 290 ppmv is chosen, the range is between 0.3 and 1 K); (ii) by comparison with the instantaneous equilibrium computations, the deeper ocean inertia induces a delay which amounts to between 6 years [for lower T _ae (2×CO₂)] and 23 years [for higher Tae(2×CO₂)] in 1980; (iii) for the standard future CO₂ and other trace gas scenarios of Wuebbles et al., the surface air warming between 1980 and 2050 is calculated to range between 0.9 and 3.4 K, with a delay amounting to between 7 years and 32 years in 2050 when compared to equilibrium computations.     

Trace gas exchange at the air/water interface: Measurements of mass accommodation coefficients

A liquid jet of 90 m diameter and variable length has been utilized to determine absorption rates and, hence, mass accommodation coefficients , of atmospheric trace gases. The compounds investigated are HCl (0.01), HNO₃ (0.01), N₂O₅ (0.005), peroxyacetyl nitrate (>0.001), and HONO (0.005). It is concluded that the absorption of these trace gases by liquid atmospheric water is not significantly retarded by interfacial mass transport. The strengths and limitations of the liquid jet technique for measuring mass accommodation coefficients are explored.     

Flow reactor and triple quadrupole mass spectrometer investigations of negative ion reactions involving nitric acid: Implications for atmospheric HNO3 detection by chemical ionization mass spectrometry

Atmospheric nitric acid measurements by ACIMS (Active Chemical Ionization Mass Spectrometry) are based on ion-molecule reactions of CO₃ ^-(H₂O) _n and NO₃ ^-(H₂O) _n with HNO₃. We have studied these reactions in the laboratory using a flow tube apparatus with mass spectrometric detection of reactant and product ions. Both product ion distributions and rate coefficients were measured. All reactions were investigated in an N₂-buffer (1–3 hPa) at room temperature. The reaction rate coefficients of OH^-, O₂ ^-, O₃ ^-, CO₄ ^-, CO₃ ^-, CO₃ ^-H₂O, NO₃ ^-, and NO₃ ^-H₂O were measured relative to the known rate k=3.0×10^-9 cm³ s^-1 for the reaction of O^- with HNO₃. The main product ion of the reaction of CO₃ ^-H₂O with HNO₃ was found to be (CO₃HNO₃)^- supporting a previous suggestion made on the basis of balloon-borne ACIMS measurements. For the reaction of bare CO₃ ^- with HNO₃ three product ions were observed, namely NO₃ ^-, (NO₃OH)^-, and (CO₃HNO₃)^-. The reaction rate coefficients for CO₃ ^-H₂O (1.7×10^-9 cm³ s^-1) and NO₃ ^-H₂O (1.6×10^-9 cm³ s^-1) were found to be close to the collision rate. The measured k values for bare CO₃ ^- (1.3×10^-9 cm³ s^-1) and NO₃ ^- (0.7×10^-9 cm³ s^-1) are somewhat smaller. The collisional dissociations of CO₃ ^-(H₂O) _n , NO₃ ^-(H₂O) _n (n=1, 2), (CO₃HNO₃)^- and (NO₃HNO₃)^-, occasionally influencing ACIMS measurements, were also studied. Fragment ion distributions were measured using a triple quadrupole mass spectrometer. The results showed that previous stratospheric nitric acid measurements were unimpaired from collisional dissociation processes whereas these processes played a major role during previous tropospheric measurements leading to an underestimation of nitric acid concentrations. Previous ACIMS HNO₃ detection was also affected by the conversion of CO₃ ^-(H₂O) _n to NO₃ ^-(H₂O) _n due to ion source-produced neutral radicals. A novel ACIMS ion source was developed in order to avoid these problems and to improve the ACIMS method.     

Determination of Dominant Pathways in Chemical Reaction Systems: An Algorithm and Its Application to Stratospheric Chemistry

The analysis of complex chemical reaction systems is frequently complicatedbecause of the coexistence of fast cyclic reaction sequences and slower pathways that yield a net production or destruction of a certain species of interest.An algorithm for the determination of both these types of reaction sequences (in a given reaction system) is presented. Under the assumption that reaction rates are known, it finds the mostimportant pathways by solving a linear optimization problem for each of them.This algorithm may be used as a tool for the interpretation of chemical model runs.For illustration, it is applied to examples in stratospheric chemistry, including the determination of catalytic ozone destruction cycles.     

On the scavenging of gaseous nitrogen compounds by large and small rain drops: II. Wind tunnel and theoretical studies of the simultaneous uptake of NH3, SO2 and CO2 by water drops

An experimental investigation of the simultaneous absorption of NH₃ and SO₂ from the ambient atmosphere by freely falling water drops has been carried out in the Mainz vertical wind tunnel. The experimental results were found to be in good agreement with the results derived from computations with the Kronig-Brink convective diffusion model and also with a model which assumes a drop to be well mixed at all times. Encouraged by this agreement, these computation schemes for the uptake of gas by single drops where incorporated in a pollution washout model with realistic SO₂, NH₃ and CO₂ gas profiles. This model allows an entire raindrop size distribution to fall through a gas layer. The results of this plume-model show that the SO₂ uptake is strongly dependent on the NH₃ concentration in the atmosphere and on the rainrate. We also find that the small drops contribute more towards the washout of these gases. In the case of simultaneous presence of NH₃ and SO₂, desorption of these gases is negligible.     

On the scavenging of SO2 by large and small rain drops: V. A wind tunnel and theoretical study of the desorption of SO2 from water drops containing S(IV)

An experimental and theoretical study has been carried out to investigate the rate of desorption of SO₂ from water drops falling at terminal velocity in air. The experiments were carried out in the Mainz vertical wind tunnel in which water drops of various sizes containing S(IV) in various concentrations were freely suspended in the vertical airstream of the tunnel. The results of these experiments were compared with the predictions of three theoretical models, and with the experiments of Walceket al. This comparison shows that the predictions of the diffusion model of Kronig and Brink in the formulation given by Walcek and Pruppacher agree well with the experimental results for all relevant large and small rain-drop sizes, and for all considered concentrations of S(IV) inside the drops. In contrast, the predictions of the diffusion model which assumes complete internal mixing inside a drop agrees with the experimental results only if the concentration of S(IV) inside the drop is less than that equivalent of an equilibrium SO₂ concentration of 15 ppbv. At larger concentrations, the theoretical predictions of the model for complete internal mixing progressively deviate from the experimental results. It is further shown that Barrie's double film model can be used to interpret the resistance to diffusion inside a drop in terms of a diffusion boundary layer inside the drop which increases in thickness with decreasing concentration of S(IV). Applying our results to the desorption of SO₂ from small and large rain drops falling below an assumed cloud base, shows that for typical contents of S(IV) inside the drops substantial amounts of SO₂ will desorb from these drops unless H₂O₂ is present in the surrounding air.     

Determination of heterogeneous reaction probability using deposition profile measurement in an annular reactor: Application to the N2O5/H2O reaction

A method for the estimation of the reaction probability of the heterogeneous N₂O₅+H₂O 2HNO₃ reaction using the deposition profile in a laminar flow tube, in which the walls are coated with the condensed aqueous phase of interest, is presented. The production of gas phase nitric acid on the surface followed by its absorption complicates the deposition profiles and hence the calculation of the reaction probability. An estimation of the branching ratio for this process enables a more appropriate calculation to be carried out. Reaction probabilities of N₂O₅ on substances including some normally constituting atmospheric aerosols, NaCl, NH₄HSO₄, as well as Na₂CO₃ are estimated and found to depend on relative humidity and characteristics of the coating used. These fell within the range (0.04–2.0)×10^–2.     

On the scavenging of SO2 by cloud and rain drops: IV. A wind tunnel and theoretical study of the absorption of SO2 in the ppb(v) range by water drops in the presence of H2O2

An experimental study involving the Mainz vertical wind tunnel is described where the rate of SO₂ removed from the air by freely suspended water drops was measured for SO₂ concentrations in the gas phase ranging between 50 and 500 ppb, and for various H₂O₂ concentrations in the liquid phase. In a first set of experiments, the pH inside the SO₂ absorbing drops was monitored by means of colour pH indicators added to the drops. In a second set of experiments, the amount of SO₂ scavenged by the drops was determined as sulfate by an ionchromatograph after the drops had been removed from the vertical air stream of the wind tunnel after various times of exposure to SO₂. The results of our experimental study were compared with the theoretical gas diffusion model of Walcek and Pruppacher which was reformulated for the case of SO₂ concentrations in the ppbv(v) range for which the main resistance to diffusion lies in the gas phase surrounding the drop. Excellent agreement between experiment and theory was obtained. Encouraged by this agreement, the theory was used to investigate the rate of sulfate production inside a drop as a function of pH. The sulfate production rate, which includes transport and oxidation, was compared with the production rate based on bulk equilibrium, as cited in the literature.     

Carbon and water flux responses to physiology by environment interactions: a sensitivity analysis of variation in climate on photosynthetic and stomatal parameters

Sensitivity of carbon uptake and water use estimates to changes in physiology was determined with a coupled photosynthesis and stomatal conductance (g _s) model, linked to canopy microclimate with a spatially explicit scheme (MAESTRA). The sensitivity analyses were conducted over the range of intraspecific physiology parameter variation observed for Acer rubrum L. and temperate hardwood C₃ (C₃) vegetation across the following climate conditions: carbon dioxide concentration 200–700 ppm, photosynthetically active radiation 50–2,000 μmol m^?2 s^?1, air temperature 5–40 °C, relative humidity 5–95 %, and wind speed at the top of the canopy 1–10 m s^?1. Five key physiological inputs [quantum yield of electron transport (α), minimum stomatal conductance (g ₀), stomatal sensitivity to the marginal water cost of carbon gain (g ₁), maximum rate of electron transport (J _max), and maximum carboxylation rate of Rubisco (V _cmax)] changed carbon and water flux estimates ≥15 % in response to climate gradients; variation in α, J _max, and V _cmax input resulted in up to ~50 and 82 % intraspecific and C₃ photosynthesis estimate output differences respectively. Transpiration estimates were affected up to ~46 and 147 % by differences in intraspecific and C₃ g ₁ and g ₀ values—two parameters previously overlooked in modeling land–atmosphere carbon and water exchange. We show that a variable environment, within a canopy or along a climate gradient, changes the spatial parameter effects of g ₀, g ₁, α, J _max, and V _cmax in photosynthesis-g _s models. Since variation in physiology parameter input effects are dependent on climate, this approach can be used to assess the geographical importance of key physiology model inputs when estimating large scale carbon and water exchange.