A model for tropospheric multiphase chemistry: application to one cloudy event during the CIME experiment

A multiphase box model for a remote environment of the troposphere has been developed with an explicit chemistry for both gas and aqueous phase. The model applied to a set of measurements performed by Voisin et al. (2000) during the European CIME experiment for a cloud event on 13th December 1997 at the top of the Puy de Dôme (France). The results of the simulation are compared to the measurements in order to follow the evolution of the ambient chemical composition as a function of the pH and of the varying water content. After verifying that the model retrieves the main features observed in the behavior of species in the cloud droplets, a detailed analysis of the simulated chemical regime is performed. It essentially discusses the sources and sinks of radical in aqueous phase, the relative importance of the oxidation pathways of volatile organic compounds by the main radicals and the conversion of S(IV) into S(VI) which seems to be influenced by the presence of peroxonitric acid, HNO₄, in aqueous phase in the environmental conditions that are considered with low H₂O₂. These numerical results are then compared with the theoretical study from Herrmann et al. (2000), who proposed a slightly different mechanism, including C2 chemistry and transition metal chemistry whereas they neglect some reaction pathways, such as the one involving OHCH₂O₂ radical. This double confrontation between model results and both real experimental data and numerical results from Herrmann et al. (1999c) underlines limitations of such modeling approach that does not include any dynamical or microphysical coupling but also demonstrates its capability to identify the main oxidants or reactants in aqueous phase in real environmental conditions more realistic than a purely theoretical approach. The originality of this study resides in the explicit and exhaustive ways the chemical reactions are treated in aqueous phase and in a first attempt to compare such a detailed chemical scheme to real environmental conditions.     

Drop size-dependent chemical composition of clouds and fogs. Part II: Relevance to interpreting the aerosol/trace gas/fog system

Size-resolved fog drop chemical composition measurements were obtained during a radiation fog campaign near Davis, California in December 1998/January 1999 (reported in Reilly et al., Atmos. Environ. 35(33) (2001) 5717; Moore et al., Atmos. Environ. this issue). Here we explore how knowledge of this size-dependent drop composition—particularly from the newly developed Colorado State University 5-Stage cloud water collector—helps to explain additional observations in the fog environment. Size-resolved aerosol measurements before and after fog events indicate relative depletion of large (>2 μm in diameter) particles during fog accompanied by a relative increase in smaller aerosol particle concentrations. Fog equivalent air concentrations suggest that entrainment of additional particles and in-fog sedimentation contributed to observed changes in the aerosol size distribution. Calculated deposition velocities indicate that sedimentation was an important atmospheric removal mechanism for some species. For example, nitrite typically has a larger net deposition velocity than water and its mass is found preferentially in the largest drops most likely to sediment rapidly. Gas–liquid equilibria in fog for NO₃⁻/HNO₃, NH₄⁺/NH₃, and NO₂⁻/HONO were examined. While these systems appear to be close to equilibrium or relative equilibrium during many time periods, divergences are observed, particularly for low liquid water content (<0.1 g m⁻³) fogs and in different drop sizes. Knowledge of the drop size-dependent composition provided additional data useful to the interpretation of these deviations. The results suggest that data from multi-stage cloud water collectors are useful to understanding fog processes as many depend upon drop size.     

Laboratory study of cluster ions formation in H2SO4–H2O system: Implications for threshold concentration of gaseous H2SO4 and ion-induced nucleation kinetics

Ion-induced binary H₂SO₄–H₂O nucleation is an important mechanism of aerosol formation in the atmosphere. Ions are created in the atmosphere mainly by galactic cosmic rays. The importance of ion-induced nucleation is recognized in some of the observed nucleation events in the background atmosphere. However, the predictions of current ion–aerosol models are highly uncertain mostly due to the lack of detailed experimental information concerning the thermodynamics and kinetics of ion clustering reactions. Here we continue the report of results of our laboratory experiments on the formation and growth of positive and negative cluster ions in H₂SO₄–H₂O vapours in the flow reactor started in Wilhelm et al. [2004. Ion-induced aerosol formation: new insights from laboratory measurements of mixed cluster ions HSO₄⁻(H₂SO₄)_a(H₂O)_w and H⁺ (H₂SO₄)_a(H₂O)_w. Atmospheric Environment 38, 1735–1744] and Sorokin et al. [2006. Formation and growth of sulphuric acid–water cluster ions: experiments, modelling, and implications for ion-induced aerosol formation. Atmospheric Environment 40, 2030–2045]. The main attention is given to the definition of the concentration of gaseous sulphuric acid in experiment and also to some aspects of the kinetics of small cluster ions formation. The performed analysis has indicated a threshold concentration of gaseous sulphuric acid for binary homogeneous nucleation of at least about 10¹⁰ cm⁻³ at room temperature and low relative humidity.     

Simulation of the tropospheric distribution of carbon monoxide during the 1984 MAPS experiment

A global, three-dimensional tropospheric chemistry model was used to perform simulations of the tropospheric distribution of carbon monoxide (CO) coinciding with NASA's Measurement of Air Pollution from Satellites (MAPS) experiment which took place during 5–13 October 1984. Archived meteorological data for September and October, 1984, were obtained from the European Centre for Medium-Range Weather Forecasting and used to drive the offline chemical transport model simulations. Base-case CO emissions were generated by applying emission factors to compiled inventories for related or co-emitted trace species. Simulation results from September and October have been compared with a recent re-release of the 1984 MAPS data and with in situ correlative data taken during the MAPS mission. Because of unrealistically large spatial variability in N₂O mixing ratios measured concurrently by MAPS, model results were also compared with an adjusted CO data set generated by assuming that errors in N₂O measured mixing ratios were correlated with errors in the MAPS CO data. These comparisons, in conjunction with simulations probing model sensitivities, led to the conclusion that biomass burning CO emissions from central and southern Africa may have been larger during September and October, 1984, than our initial best estimate based on the CO₂ emissions data of Hao et al. (1990. Fire in the Tropical Biota; Ecosystem Processes and Global Challenges. Springer, Berlin, pp. 440–462; 1994. Global Biogeochemical Cycles 8, 495–503). This result is in disagreement with recent estimates of biomass burning emissions from Africa (Scholes et al., 1996, Journal of Geophysical Research 101, 23677–23682) which are smaller than previously thought for emissions from this region. Although unknown model deficiencies cannot be conclusively ruled out, model sensitivity studies indicate that increased CO emissions from central and southern Africa offer the best explanation for reducing observed differences between model results and MAPS data for this time period. Our results, in combination with a disparity in recent CO emission estimates from this region (Scholes et al., 1996; Hao et al., 1996, Journal of Geophysical Research 101, 23577–23584), and in light of recent indications of highly variable biomass burning activities from the tropical western Pacific (Folkins et al., 1997, Journal of Geophysical Research 102, 13291–13299), seem to suggest that biomass burning emissions exhibit significant year-to-year variability. This large variability of emissions sources makes the accurate simulation of specific time periods very difficult and suggests that biomass burning trace species inventories may have to be developed specifically for each simulated time period, employing satellite-derived information on fire coverage and flame intensity.     

A comparison of models to estimate in-canopy photosynthetically active radiation and their influence on canopy stomatal resistance

The models for photosynthetically active radiation (PAR) used in a multi-layer canopy stomatal resistance (CSR) model developed by Baldocchi et al. (Atmospheric Environment 21 (1987) 91–101) and in a two-big-leaf CSR model developed by Hicks et al. (Water, Air and Soil Pollution 36 (1987) 311) are investigated in this study. The PAR received by shaded leaves in Baldocchi et al. (1987) is found to be larger than that predicted by a canopy radiative-transfer model developed by Norman (in: Barfield, Gerber, (Eds.), Modification of the Aerial Environment of Crops. ASAE Monograph No. 2. American Society for Agricultural. Engineering, St. Joseph, MI, 1979, p. 249) by as much as 50% even though the Baldocchi et al. (1987) model is indirectly based on Norman's model. This larger value of PAR results in turn in a smaller CSR by as much as 30% for canopies with larger leaf area indexes. A new formula to predict vertical profiles for PAR received by shaded leaves inside a canopy is suggested in the present study based on Norman (1979) and agrees well with the original model of Norman (1979). The simple treatment used in Hicks et al. (1987) for canopy-average PAR received by shaded leaves is found to diverge for canopies with leaf area indexes not close to two A new empirical formula for canopy-average PAR is then suggested for use in a two-big-leaf model, and it is shown that under most conditions the modified two-big-leaf CSR model can predict reasonable values when compared with the more complex multi-layer CSR model. Both the modified multi-layer CSR model and the modified two-big-leaf CSR model are also shown to predict reasonable dry deposition velocities for O₃ when compared to several sets of measurements.     

Measurement of Ozone Concentration

A method based on hourly NWS cloud amount reports is presented for developing a simple model to account for cloud cover in the determination of the nitrogen dioxide photolysis rate constant, k ₁ The model is parameterized and verified with direct UV radiometer and k ₁ measurements (vs. time of day) collected by Sickles, et al. ¹ at Research Triangle Park. Application of our model to variable cloud condition situations indicates that significant improvement in k ₁ prediction is obtained by including the influence of cloud cover. Comparison of our model with the radiative transfer calculations of Peterson⁷ indicates that the particular parameterization of k ₁ given here is most representative of average albedo and relatively heavy aerosol loading conditions. Comparison of ozone predictions using hourly averaged k ₁ and instantaneous k ₁ under conditions of varying cloud cover suggest that the errors resulting from averaging k ₁ are largest when variations in solar zenith angle are significant over the hour.     

Intercomparison of measurement methods for black carbon aerosols

In this study, two method intercomparisons were performed. One thermal and two optical methods for the measurement of black carbon (BC) were applied to laboratory generated aerosols containing only BC. For the optical measurements, an aethalometer (Hansen et al., 1984. Science of Total Environment 36, 191–196) and an integrating sphere technique (Hitzenberger et al., 1996b. Journal of Geophysical Research 101, D14, 19 601–19 606) were used. The thermal method was described by Cachier et al. (1989a. Tellus 41B, 379–390). In an additional comparison, the integrating sphere was compared to a thermal optical technique (Birch and Cary, 1996. Aerosol Science Technology 25, 221–241) on ambient aerosol samples. The absorption coefficients were obtained from transmission measurements on filter samples for both the aethalometer and the integrating sphere. The BC mass concentration for the aethalometer was derived from this absorption measurement. The BC mass concentration for the integrating sphere, however, was obtained using an independent calibration curve. The agreement between the absorption coefficient σ_a obtained for the BC test aerosol on parallel filters with the aethalometer and the integrating sphere was satisfactory. The slope of the regression lines depended on filter type. A comparison between BC mass concentrations, however, showed that the aethalometer values were only 23% of those obtained by the integrating sphere technique indicating that for pure BC aerosols, the standard aethalometer calibration should not be used. Compared to the thermal method, the integrating sphere gave an overestimation of the BC mass concentrations by 21%. For the ambient samples, the integrating sphere and the thermal optical methods for BC mass concentration determination showed agreement within 5% of the 1 : 1 line, although the data were not so well correlated.     

Sampling and chemical analysis of ice crystals as a function of size

Size-classified ice crystal samples were collected during the Spring of 1998, at the Jungfraujoch High-Alpine Research Station (3454 m), located in Switzerland. A procedure modified from the Guttalgor method, originally developed for size-selective sampling of raindrops by Bächmann et al. (Atmos. Environ. 26A (1992) 1795) was used to sample ice crystals during precipitation events. The size-classified ice crystal samples were analyzed using ion chromatography to determine the concentrations of Na⁺, NH₄⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, NO₃⁻, and SO₄²⁻ in each size class. For ions associated with coarse mode aerosol, Na⁺, K⁺, Ca²⁺, Mg²⁺, and Cl⁻, concentration increased with decreasing ice crystal size, suggesting scavenging by nucleation. For the remaining ions, mixed behavior was observed suggesting a combination of gas phase scavenging and scavenging via riming.     

A risk assessment of potential agricultural losses due to ambient SO2 in the central regions of Chile

A risk assessment of the potential impacts of sulphur dioxide (SO₂) on the agriculture of central Chile was carried out, using Critical Levels (threshold values above which chronic effects may occur) set by the United Nations Economic Commission for Europe (UNECE, 1993; Sanders et al., 1995), crop sensitivity studies, agricultural land-use data, and air quality data for several years. Ambient SO₂ concentrations around three copper smelters in this region were found to pose a significant risk to crops (such as cereals, staples and legumes) on both local and regional scales. Adverse effects on yield, growth and fruit production were considered possible. Frequent high exposure periods during winter months may also give rise to acute injury in sensitive species and/or crops maintained under optimum water conditions. This study identified high-risk areas, where additional monitoring as well as field studies would be beneficial, and has important policy implications, given the secondary SO₂ air quality standard currently in force in Chile.     

Methane in the Atmosphere

Methane is present in the troposphere with a volume concentration of about 1.5 ppm. Estimates of Koyama (1963) indicate a predominantly biological origin with a total production rate of about 2.7 × 10¹⁴ g CH₄/yr. From that he estimated the atmospheric lifetime of methane to be around 20 years. Measurements of the C-l4 in methane by Libby and later by Bainbridge, et al. (1961 ) gave a C-l4 content of 75% of recent wood and, therefore, confirm the predominant biological origin, the addition of inactive CH; from industrial sources being only about 25%. Much less is known about sinks of CH₄. Cadle (1966) reported fairly high destruction rates by atomic O, a reaction which should be important at high altitude. Bainbridge (1966) indeed reports a decrease in the measured methane concentration above the tropopause. He, however, considers this decrease too small to account for the destruction rate of 20 years estimated by Koyama. Our measurements on air samples collected on aircraft flights at various altitudes show a high variability of the CH₄ content both with time and altitude.     

Comment on “Gaseous Sulfur Pollutants from Urban and Natural Sources”

An analysis has been performed of data on particle samplers obtained during 1984 at Rubidoux, California, and Phoenix, Arizona, by the U.S. EPA, with emphasis on prediction of mass collected by the Andersen model 321A and Wedding inlet (previously GMW40CFM) PM₁₀ samplers. The recent interpretation of these data by Rodes et al. ¹ appears to fail to correct adequately for particle bounce, and to severely overestimate the FINE particle mass. The present study uses two completely different algorithms to make these corrections. The results obtained from these two approaches agree within a few percent, and lead to a prediction of the mass collected by the Wedding inlet within 7 percent. The Andersen 321A sampler, on the other hand, overcollects by as much as 34 percent. This analysis, if substantiated, would raise serious questions concerning the adequacy of the presently proposed Federal Reference Method for qualification of PM₁₀ samplers.     

Fully coupled “online” chemistry within the WRF model

A fully coupled “online” Weather Research and Forecasting/Chemistry (WRF/Chem) model has been developed. The air quality component of the model is fully consistent with the meteorological component; both components use the same transport scheme (mass and scalar preserving), the same grid (horizontal and vertical components), and the same physics schemes for subgrid-scale transport. The components also use the same timestep, hence no temporal interpolation is needed. The chemistry package consists of dry deposition (“flux-resistance” method), biogenic emission as in [Simpson et al., 1995. Journal of Geophysical Research 100D, 22875–22890; Guenther et al., 1994. Atmospheric Environment 28, 1197–1210], the chemical mechanism from RADM2, a complex photolysis scheme (Madronich scheme coupled with hydrometeors), and a state of the art aerosol module (MADE/SORGAM aerosol parameterization).The WRF/Chem model is statistically evaluated and compared to MM5/Chem and to detailed photochemical data collected during the summer 2002 NEAQS field study. It is shown that the WRF/Chem model is statistically better skilled in forecasting O₃ than MM5/Chem, with no appreciable differences between models in terms of bias with the observations. Furthermore, the WRF/Chem model consistently exhibits better skill at forecasting the O₃ precursors CO and NO_y at all of the surface sites. However, the WRF/Chem model biases of these precursors and of other gas-phase species are persistently higher than for MM5/Chem, and are most often biased high compared to observations. Finally, we show that the impact of other basic model assumptions on these same statistics can be much larger than the differences caused by model differences. An example showing the sensitivity of various statistical measures with respect to the treatment of biogenic volatile organic compounds emissions illustrates this impact.     

Traffic pollution in a downtown site of Buenos Aires City

It has recently been recognized that air and noise pollution constitutes an extended problem over the densely populated city of Buenos Aires. Traffic emissions are of paramount concern, especially along narrow and main traffic arteries. In spite of these considerations, few systematic studies have been undertaken to evaluate the air quality in the metropolitan area of the city. In 1996, concentrations of carbon monoxide (CO), nitric oxide (NO), nitrogen dioxide (NO₂) and ozone (O₃) were simultaneously measured for the first time using a continuous monitoring station. This station was placed in a building at Belgrano Avenue, which is a heavy traffic street in the downtown area of the city (Bogo et al., Atmospheric Environment 33 (1999) 2587. In this work, we analyze the dependence of the measured primary pollutants, CO and the mixture of nitrogen oxides (NO_x), with meteorological conditions, traffic emissions and monitoring location. We compare the registered values with the results obtained from modeling the dispersion of the pollutants emitted from mobile and area sources. We also discuss the relevance of street canyon effects compared with background concentrations of these pollutants.     

Continuous integration in urban social-ecological systems science needs to allow for spacing co-existence: This article belongs to Ambio’s 50th Anniversary Collection. Theme: Urbanization

Urbanization brings benefits and burdens to both humans and nature. Cities are key systems for integrated social-ecological research and the interdisciplinary journal of Ambio has published ground-breaking contributions in this field. This reflection piece identifies and discusses integration of the human and natural spheres in urban social-ecological research using the following foundational papers as important milestones: Folke et al. (1997), Ernstson et al. (2010) and Andersson et al. (2014). These papers each take unique approaches that aim to uncover core properties—processes, structures, and actors—of urban systems and set them into mutual relationship. This piece will end with a forward-looking vision for the coming 50 years of urban sustainability and resilience study in Ambio.     

The Correlation between Light Scattering and Mass Concentration of Tobacco Smoke

Reports by others^1,2 have pointed to tobacco smoke as a significant source of air pollution in indoor spaces. Studies by Charlson, et al., ³ Kretzschmar,⁴ and Eccleston, et al. ⁵ have yielded mass concentration-light scattering correlations for several natural aerosols. This note presents a value for the mass concentration/ light scattering ratio for tobacco smoke. This ratio provides a means of assessing air quality in indoor spaces using an instrument with a fairly short (?1 min) time constant.     

Mechanochemical destruction of mirex co-ground with iron and quartz in a planetary ball mill

Mechanochemical destruction (MCD) has been recognized as a promising non-combustion technology for the disposal of obsolete pesticides belonging to the persistent organic pollutants (POPs). Mirex, a termiticide ever used for many years in China, was ball milled in the presence of various reagent(s) in a planetary ball mill at room temperature to investigate the destruction efficiency. The ground samples were characterized and analyzed by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, gas chromatography (GC), and ion chromatography (Martins, Bicego et al.). Under the same conditions of mill rotary rate and charge ratio, the mixture of iron powder and quartz sand (Fe/SiO₂) was found best in promoting the mirex destruction. Mirex was completed destroyed after 2 h grinding at a charge ratio of 36:1 (reagent/mirex, m/m) and a mill rotation speed of 550 rpm. No organic compound was detected by GC/μECD screening. The yield of water-soluble chlorine determined by ion chromatography (Martins, Bicego et al.) in the final residue accounted for 90.7% of chlorine in the original mirex, which indicated a nearly complete dechlorination. Signals of both graphite and amorphous carbon were found in the Raman spectra of the co-ground powder samples. With the main final degradation products of water soluble Cl and carbon, the mechanism of the mechanochemical destruction approach should be dechlorination followed by the carbonization.     

Evaluation of SO2 dry deposition over short vegetation in Portugal

SO₂ dry deposition was studied over short vegetation, in Portugal, by means of the concentration gradient method. The experimental study involved one first phase of long-term measurements carried out in a grassland and, subsequently, a second period of several 1997 intensive field campaigns performed in three places representing different climate and surface conditions. Temporal and spatial patterns of dry deposition parameters show that downward fluxes of SO₂ are by some extent affected by surface processes. Median R_c varied from 140 s cm⁻¹ to values around 200 s cm⁻¹, in a wide range of environmental conditions. Stomatal uptake is an important sink when vegetation is biologically active, but its contribution is effectively low when compared with non-stomatal mechanisms, especially when the surface is wet. Under dry conditions R_c increases by a factor of two, but SO₂ deposition rates then still are significant. The parameterisation of the surface resistance for SO₂ proved to be difficult, but V_d derived with the Erisman parameterisation (Erisman et al., Atmos. Environ. 28 (16) (1994) 2595) compared best with measured values, at low time resolution scale and especially under moisture conditions.     

Probing the sensitivity of gaseous Br2 production from the oxidation of aqueous bromide-containing aerosols and atmospheric implications

This paper presents a global sensitivity and uncertainty analysis of the bromine chemistry included in the Model of Aqueous, Gaseous and Interfacial Chemistry (MAGIC) in dark and photolytic conditions. Uncertainty ranges are established for input parameters (e.g. chemical rate constants, Henry's law constants, etc.) and are used in conjunction with Latin hypercube sampling and multiple linear regression to conduct a sensitivity analysis that determines the correlation between each input parameter and model output. The contribution of each input parameter to the uncertainty in the model output is calculated by combining results of the sensitivity analysis with input parameters' uncertainty ranges. Model runs are compared using the predicted concentrations of molecular bromine since Br_2(g) has been shown in previous studies to be generated via an interface reaction between O_3(g) and Br_(surface)^? during dark conditions [Hunt et al., 2004]. Formation of molecular bromine from the reaction of ozone with deliquesced NaBr aerosol: evidence for interface chemistry. Journal of Physical Chemistry A 108, 11559–11572]. This study also examines the influence of an interface reaction between OH_(g) and Br_(surface)^? in the production of Br_2(g) under photolytic conditions where OH_(g) is present in significant concentrations. Results indicate that the interface reaction between O_3(g) and Br_(surface)^? is significant and is most responsible for the uncertainty in MAGICs ability to calculate precisely Br_2(g) under dark conditions. However, under photolytic conditions the majority of Br_2(g) is produced from a complex mechanism involving gas-phase chemistry, aqueous-phase chemistry, and mass transport.     

A DFT study of the reactions of O3 with Hg° or Br

In the mid 1980s the study of ozone reactivity gained a significant interest with the discoveries of the stratospheric ozone hole (Farman et al., 1985) and of the ozone depletion events in the polar boundary layer (Oltmans et al., 1989). In the stratosphere, the mechanism involves heterogeneous reactions on polar stratospheric clouds that lead to chlorine activation (Solomon et al., 1986). In contrast, tropospheric ozone depletion occurring during polar springtime rather involves reactive bromine species. They are released during a series of photochemical and heterogeneous reactions often called the bromine explosion (see the review of Simpson et al., 2007). In this reaction sequence, an essential step is the generation of photolyzable Br₂, the precursor of two Br atoms, via the multiphasic reaction (1):

(1)

HOBr + Br⁻ + H⁺ → H₂O + Br₂

The production of reactive HOBr could occur with the oxidation of BrO by HO₂.