Elevational patterns of sulfur deposition at a site in the Catskill Mountains,New York

In this paper we report measurements of SO^2-₄ fluxes in throughfall and bulk deposition across an elevational transect from 800 to 1275 m on Slide Mountain in the Catskill Mountains of southeastern New York State. The net throughfall flux of SO^2-₄ (throughfall-bulk deposition), which we attribute to cloud and dry deposition, increased by roughly a factor of 13 across this elevational range. Part of the observed increase results from the year-round exposure of evergreen foliage at the high-elevation sites, compared to the lack of foliage in the dormant season in the deciduous canopies at low elevations. Comparison of the net throughfall flux with estimates of cloud deposition suggests that both cloud deposition and dry deposition increased with elevation. Dry deposition estimates from a nearby monitoring site fall within the measured range of net throughfall flux for SO^2-₄. The between-site variation in net throughfall flux was very high at the high-elevation sites, and less so at the lower sites, suggesting that studies of atmospheric deposition at high-elevations will be complicated by extreme spatial variability in deposition rates. Studies of atmospheric deposition in mountainous areas of the eastern U.S. have often emphasized cloud water deposition, but these results suggest that elevational increases in dry deposition may also be important.     

Estimates of cloud water deposition at Mountain Acid Deposition Program sites in the Appalachian Mountains

Cloud water deposition was estimated at three high-elevation sites in the Appalachian Mountains of the eastern United States (Whiteface Mountain, NY; Whitetop Mountain, VA; and Clingman's Dome, TN) from 1994 through 1999 as part of the Mountain Acid Deposition Program (MADPro). This paper provides a summary of cloud water chemistry, cloud liquid water content, cloud frequency, estimates of cloud water deposition of sulfur and nitrogen species, and estimates of total deposition of sulfur and nitrogen at these sites. Other cloud studies in the Appalachians and their comparison to MADPro are also summarized. Whiteface Mountain exhibited the lowest mean and median concentrations of sulfur and nitrogen ions in cloud water, while Clingman's Dome exhibited the highest mean and median concentrations. This geographic gradient is partly an effect of the different meteorological conditions experienced at northern versus southern sites in addition to the difference in pollution content of air masses reaching the sites. All sites measured seasonal cloud water deposition rates of SO4(2-) greater than 50 kg/ha and NO3(-) rates of greater than 25 kg/ha. These high-elevation sites experienced additional deposition loading of SO4(2-) and NO3(-) on the order of 6-20 times greater compared with lower elevation Clean Air Status and Trends Network (CASTNet) sites. Approximately 80-90% of this extra loading is from cloud deposition.     

Emission Strength Validation Using Four-Dimensional Data Assimilation: Application to Primary Aerosol and Precursors to Ozone and Secondary Aerosol

ABSTRACT

Three-dimensional air quality models (AQMs) represent the most powerful tool to follow the dynamics of air pollutants at urban and regional scales. Current AQMs can account for the complex interactions between gas-phase chemistry, aerosol growth, cloud and scavenging processes, and transport. However, errors in model applications still exist due in part to limitations in the models themselves and in part to uncertainties in model inputs. Four-dimensional data assimilation (FDDA) can be used as a top-down tool to validate several of the model inputs, including emissions inventories, based on ambient measurements. Previously, this FDDA technique was used to estimate adjustments in the strength and composition of emissions of gas-phase primary species and O₃ precursors.

In this paper, we present an extension to the FDDA technique to incorporate the analysis of particulate matter (PM) and its precursors. The FDDA approach consists of an iterative optimization procedure in which an AQM is coupled to an inverse model, and adjusting the emissions minimizes the difference between ambient measurements     

Cumulus cloud transport,scavenging and chemistry: Observations and simulations

Observational and numerical investigations of cumulus cloud scavenging, transport and chemical processes are presented. The experimental data set includes surface and aircraft measurements of the chemistry and microphysics of aerosol, cloud and precipitation. To help in the interpretation of these experimental data fully three-dimensional simulations of cloud chemistry and scavenging are performed. After adjusting several unmeasured model parameters, reasonable agreement could be obtained between the simulated and observed cloud chemistry and aerosol distribution in clouds. The rate at which the simulated clouds transported and transformed pollutants did not exceed a few per cent per hour.     

Coupling quasi-spectral microphysics with multiphase chemistry: a case study of a polluted air mass at the top of the Puy de Dôme mountain (France)

An explicit multiphase chemistry model (Atm. Environ. 34 (29/30) (2000) 5015) has been coupled with quasi-spectral microphysics, based upon Berry and Reinhardt's parameterizations (1974a, b). This coupled model has been initialized with polluted conditions as observed at the Puy de Dôme mountain in the center of France and for a maritime cloud.The presence of clouds results in two effects on multiphase chemistry: a direct effect through mass transfer, solubility and reactivity, and an indirect effect through microphysical transfer from cloud water into rainwater and redistribution of reactive soluble species among interstitial air, cloud droplets and raindrops.Results demonstrate that microphysical processes are necessary to sketch out the complex, nonlinear multiphase chemistry in a real cloud. In addition to the direct exchange through mass transfer, incorporation of reactive oxidants such as HO_x in droplets can arise and consequently make those species no longer available for reacting in the gas-phase. Moreover, microphysical coalescence conversions favor NO_x destruction and enhance the chemical nitric acid production. Coalescence of cloud drops to form rain transfers dissolved species into drops that are undersaturated compared to Henry's law equilibrium. The rain becomes a reservoir for these species, allowing aqueous chemistry to produce more nitric acid than would be possible without the presence of rain.Finally, for the different cloud types, the fate of those intermediate and reactive species is investigated, looking at their budget in clear sky situation versus cloudy and/or rainy situations.     

Prediction of the Vertical Profile of Ozone Based on Ground-Level Ozone Observations and Cloud Cover

Abstract

A number of statistical techniques have been used to develop models to predict high-elevation ozone (O₃) concentrations for each discrete hour of day as a function of elevation based on ground-level O₃ observations. The analyses evaluated the effect of exclusion/inclusion of cloud cover as a variable. It was found that a simple model, using the current maximum ground-level O₃ concentration and no effect of cloud cover provided a reasonable prediction of the vertical profile of O₃, based on data analyzed from O₃ sites located in North Carolina and Tennessee. The simple model provided an approach that estimates the concentration of O₃ as a function of elevation (up to 1800 m) based on the statistical results with a ±13.5 ppb prediction error, an R² of 0.56, and an index of agreement, d ₁, of 0.66. The inclusion of cloud cover resulted in a slight improvement in the model over the simple regression model. The developed models, which consist of two matrices of 24 equations (one for each hour of day for clear to partly cloudy conditions and one for cloudy conditions), can be used to estimate the vertical O₃ profile based on the inputs of the current day’s 1-hr maximum ground-level O₃ concentration and the level of cloud cover.     

Time study of trace elements and major ions during two cloud events at the Mt. Brocken

Cloud water investigations have been performed at the highest elevation of Central Germany in 1997. Results of extensive trace element measurements are presented. Besides conductivity, pH, liquid water content and major ions the data set includes 49 minor and trace elements. Estimation of crustal enrichment factors (EFs) provides an indication of the anthropogenic contributions to the cloud water concentrations. The variation of cloud composition with time has been illustrated for two selected events with different air mass origins. The chemical composition of the cloud condensation nuclei on which the droplets grow mainly determines the cloud water chemistry. For a cloud event in June 1997 the concentrations of the crustally derived elements Si, Al, Fe, Ti, Ce, La and Nd follow each other closely. The fact that SO₄²⁻, NO₃⁻ and NH₄⁺ are only moderately correlated with the particular pollutants with high enrichment factors such as Cd, Sb, Pb, Zn, Cu, As, Bi, Sn, Mo, Ni, Tl and V indicates that their source regions are more widespread. During an event in October 1997 the time trends for most minor and trace elements follow rather closely those for the major ions NH₄⁺, SO₄²⁻ and NO₃⁻. Back trajectories show that the transport from continental and marine European sources was the likely cause of the sample concentrations. EFs of trace elements in cloud water samples during the June and October event show a strong correlation with those obtained for urban particulate matter. Although both events are influenced by air masses of different origin, there is a good agreement between the EF signatures.     

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.     

Wintertime Vertical Variations in Particulate Matter (PM) and Precursor Concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Abstract

Air quality monitoring was conducted at a rural site with a tower in the middle of California’s San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM₁₀/M_2.5 Air Quality Study. Measurements at the surface and on a tower at 90 m were collected in Angiola, CA, from ecember 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO₂ appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM_2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.     

Numerical studies of acidification processes within and below clouds with a flow-through chemical reactor model

A flow-through chemical reactor model has been exercised to assess the importance of various oxidation reactions and cloud processes on wet removal and redistribution of atmospheric pollutants and to investigate the effect of in-cloud acidification on precipitation chemistry at the surface. Preliminary results indicate that in-cloud acidification accounts for more than 60% of the wet deposited acids derived from acidification of initial SO₂, that 42–57% of water-soluble, non-reactive NH₃ and HNO₃ are removed by wet deposition. The pseudo-first-order conversion rate of SO₂ to SO₄²⁻ ranges from 3 to 25% h ⁻¹ depending on initial and boundary conditions.Sensitivity studies have been carried out to test the importance of time evolution of clouds on partitioning of pollutants in the atmosphere and to investigate the variability of precipitation chemistry due to changes in rate constants. The distributions of NH₃ and HNO₃ are found to be dependent largely on the cloud microphysical parameters, while the distributions of H₂O₂ and SO₂ depend largely on initial conditions of both species. Individual physical and chemical mechanisms can determine the overall rate of sulfate wet deposition at different stages of cloud evolution.     

The relation between ozone,NOx and hydrocarbons in urban and polluted rural environments

Research over the past ten years has created a more detailed and coherent view of the relation between O₃ and its major anthropogenic precursors, volatile organic compounds (VOC) and oxides of nitrogen (NO_x). This article presents a review of insights derived from photochemical models and field measurements. The ozone–precursor relationship can be understood in terms of a fundamental split into a NO_x-senstive and VOC-sensitive (or NO_x-saturated) chemical regimes. These regimes are associated with the chemistry of odd hydrogen radicals and appear in different forms in studies of urbanized regions, power plant plumes and the remote troposphere. Factors that affect the split into NO_x-sensitive and VOC-sensitive chemistry include: VOC/NO_x ratios, VOC reactivity, biogenic hydrocarbons, photochemical aging, and rates of meteorological dispersion. Analyses of ozone–NO_x–VOC sensitivity from 3D photochemical models show a consistent pattern, but predictions for the impact of reduced NO_x and VOC in indivdual locations are often very uncertain. This uncertainty can be identified by comparing predictions from different model scenarios that reflect uncertainties in meteorology, anthropogenic and biogenic emissions. Several observation-based approaches have been proposed that seek to evaluate ozone–NO_x–VOC sensitivity directly from ambient measurements (including ambient VOC, reactive nitrogen, and peroxides). Observation-based approaches have also been used to evaluate emission rates, ozone production efficiency, and removal rates of chemically active species. Use of these methods in combination with models can significantly reduce the uncertainty associated with model predictions.     

SOA from methylglyoxal in clouds and wet aerosols: Measurement and prediction of key products

Aqueous OH radical oxidation of methylglyoxal in clouds and wet aerosols is a potentially important global and regional source of secondary organic aerosol (SOA). We quantify organic acid products of the aqueous reaction of methylglyoxal (30–3000 μM) and OH radical (approx. 4 × 10^?12 M), model their formation in the reaction vessel and investigate how the starting concentrations of precursors and the presence of acidic sulfate (0–840 μM) affect product formation. Predicted products were observed. The predicted temporal evolution of oxalic acid, pyruvic acid and total organic carbon matched observations at cloud relevant concentrations (30 μM), validating this methylglyoxal cloud chemistry, which is currently being implemented in some atmospheric models of SOA formation. The addition of sulfuric acid at cloud relevant concentrations had little effect on oxalic acid yields. At higher concentrations (3000 μM), predictions deviate from observations. Larger carboxylic acids (≥C₄) and other high molecular weight products become increasingly important as concentration increases, suggesting that small carboxylic acids are the major products in clouds while larger carboxylic acids and oligomers are important products in wet aerosols.     

Cloud Albedo,Greenhouse Effects,Atmospheric Chemistry,and Climate Change

Changes in global atmospheric chemistry and climate are taking place as a result of observed trends in long-lived species such as CO₂, CH₄, N₂O, and the CFCs. The continuation of these trends is expected to eventually lead to a major atmospheric warming that might profoundly affect the society we live in. Trends in short-lived species such as NOx and SOx are also suspected. These trends are not as well established, because the shorter-lived species vary spatially and temporally. Trends in NOx would be expected to lead to increases in tropospheric ozone that would add to the warming created by the other greenhouse gases. Trends in NOx could also alter tropospheric OH concentrations that could lead to changes in CH₄ and some of the CFCs. On the other hand, increases in sulfur emissions may alter cloud optical properties. The changes in cloud optical properties could possibly offset the warming expected from increases in greenhouse gases, depending on the role of natural oceanic sulfur emissions. This paper summarizes recent research in these areas and the interactions of climate and atmospheric chemistry.     

Models for gas/particle partitioning,transformation and air/water surface exchange of PCBs and PCDD/Fs in CMAQ

We have added the capability to simulate polychlorinated biphenyls (PCBs) and polychlorinated dibenzo [p] dioxins and polychlorinated dibenzo-furans (PCDD/Fs) to the Community Multiscale Air Quality (CMAQ) modeling system, thus taking advantage of the latter's capability to simulate atmospheric advection, diffusion, gas-phase chemistry, cloud/precipitation, and aerosol processes. The modifications reported here include the addition to the CMAQ system of two gas/particle partitioning models options: the Junge–Pankow adsorption model and the K_OA absorption model, as well as chemical transformations and atmosphere/water surface exchange processes for these semi-volatile organics. Simulations for the purpose of model testing and validation were conducted for the years 2000 and 2002 on a domain covering most of North America. Both partitioning models give reasonable results when compared with available measurements. The model predictions of deposition and air concentrations also agree well with measurements. The modeling results also indicate that the long-range transport is important and anthropogenic emissions of PCBs and PCDD/Fs are dominant although surface exchange of PCBs may be important for some clean locations.     

Cloud chemistry in the eastern United States, as sampled from three high-elevation sites along the Appalachian Mountains

Atmospheric deposition of acidic cloud water is thought to be one of the causes for the recent forest decline in industrialized areas of the world. The present paper presents results from the Mountain Acid Deposition Program (MADPro), a part of EPA's Clean Air Status and Trends Network, (CASTnet). We used automated cloud water collectors at three selected mountain sites (Whiteface Mt., NY; Whitetop Mt., VA; and Clingman's Dome, TN) to take hourly samples from non-precipitating clouds during temperate (non- freezing) seasons of each year from 1994 to 1997. Samples were promptly analyzed for pH, conductivity, and concentration of dissolved ions. Cloud liquid water content (LWC) and meteorological parameters were measured at each site. Mean cloud frequencies and LWC of clouds were higher at Whiteface Mt., NY, than in the Southern Appalachians. The four most prevalent ions found in cloud water samples were usually, in order of decreasing concentration: sulfate (SO²⁻₄) hydrogen (H⁺), ammonium (NH₄⁺), and nitrate (NO₃⁻). Within cloud events the concentration of these major ions tended to co-vary. Typically there was an inverse relationship between LWC of the cloud and ionic concentration of the cloud water. During the sampling season, the highest ionic concentrations were seen during mid-summer. Ionic concentrations of samples from the southern sites were significantly higher than samples from Whiteface Mt., but further analysis indicates that this is at least partially due to the north–south difference in the LWC of clouds. MADPro results are shown to be comparable with previous studies of cloud chemistry in North America.     

A computer modelling study of the chemistry occurring during cloud formation over hills

A model has been developed which describes the chemical processes occurring during the formation of hill cloud. This model has been applied to the study of four cases which should be typical of the chemical conditions which can exist during the formation of such cloud over hills in the N of England.The results show that a wide range of chemical behaviour is possible in cloud droplets, depending on the history of the airmass. The composition of the water-soluble aerosol is of importance in determining the chemical composition of cloud droplets, with most of the sulphate and large proportions of the other ions being derived from this source. Gas-phase chemistry is also important, not only because it dictates the initial concentrations of oxidants such as H₂O₂ and O₃ and of acidic gases such as HNO₃ at the onset of condensation, but also because of the chemical processes which occur concurrently with those in clouds. These are important sources of radicals, as well as of nitric acid, which continue to dissolve in solution. Gasphase HCl, HNO₃ and NH₃ are all of primary importance in describing the acidity of cloud droplets. The various oxidation mechanisms for SO₂ can all be important, with their relative contributions varying from case to case. H₂O₂ does not invariably dominate this process, especially in winter when its concentration may be low.The chemistry of hill clouds is far from trivial and oversimplification can result in a misunderstanding of the behaviour which occurs. There is a need, rather, to consider a wide range of reactions if the nature of the overall processes and the impact of manmade emissions on the environment via this route are to be understood.     

A model of wet deposition to complex terrain

A two dimensional model of the seeder-feeder mechanism of orographic rainfall enhancement has been developed. The model has been extended to include the deposition of aerosol material incorporated into the orographic feeder cloud by nucleation scavenging. Parameterizations of any changes in the concentration of SO₄²⁻ in the cloud due to chemical reactions have also been included. The model is used to predict the rainfall enhancement and SO₄²⁻ deposition over terrain consisting of two parallel ridges oriented perpendicular to the wind. A wide range of spatial scales has been used of up to 150 km. It is found that the patterns of rainfall enhancement and deposition are strongly dependent on the spatial scales, the atmospheric structure and the cloud chemistry.     

Organosulfates from glycolaldehyde in aqueous aerosols and clouds: Laboratory studies

Secondary organic aerosol (SOA) formation is enhanced on acidic seed particles; SOA also forms during cloud processing reactions where acidic sulfate is prevalent. Recently several studies have focused on the identification of organosulfates in atmospheric aerosols or smog chamber experiments, and upon the mechanism of formation for these products. We identify several organosulfate products formed during the laboratory OH radical oxidation of dilute aqueous glycolaldehyde in the presence of sulfuric acid. We propose a radical–radical reaction mechanism as being consistent with formation of these products under our experimental conditions. Using a kinetics model we estimate that organosulfates account for less than 1% of organic matter formed from these precursors during cloud processing. However, in wet acidic aerosols, where precursors are highly concentrated and acidic sulfate makes up close to half of the aerosol mass, this radical–radical reaction could account for significant organosulfate production.     

Impact of radical versus non-radical pathway in the Fenton chemistry on the iron redox cycle in clouds

Modeling studies have shown that the Fenton reaction of iron(II) with H2O2 can contribute, in a significant amount, to OH radicals production in cloud droplets. However, the destruction mechanism of hydrogen peroxide by iron(II) is still uncertain. Two reaction pathways for the first step of Fenton chemistry have been advanced: a radical pathway which considers an OH radical production and a non-radical pathway considering ferryl ion production. The aim of this work is to evaluate the impact of these two possible reaction pathways for Fenton chemistry on the iron redox cycle in cloud droplets. For this purpose, the numerical model of multiphase chemistry M2C2 has been applied to a rural chemical scenario representative of continental conditions. This study highlights that the iron redox cycling is driven by Fenton reaction whatever Fenton mechanism is considered. The ferryl ion chemistry becomes significant in the iron redox cycling when this species is considered as an active intermediate in Fenton chemistry and under night time conditions the iron redox chemistry is controlled by the ferryl ion reactivity. The partitioning of iron between its two main oxidation states (+II and +III) in cloud droplets, which is the indicator of the iron oxido-reduction potential, does not change significantly between the two cases. However, for the non-radical case, the ferryl ion concentration is up to four orders of magnitude higher than the OH concentration highlighting its potential role in oxidative capacity of cloud droplets.