Monitoring the dry deposition of SO2 in the Netherlands: Results for grassland and heather vegetation

An automated system based on the micrometeorological gradient technique has been developed to measure the dry deposition of SO₂ on a routine basis. Measurements were made at two locations in the Netherlands. From these results dry deposition fluxes, dry deposition velocities and surface resistances for a heathland and for an agricultural grassland site were estimated using a selected set of data and a calculation procedure based on micrometeorological considerations. An extensive analysis was made to determine uncertainties in the resulting deposition parameters. From this analysis it has been concluded that the uncertainty in these parameters is almost completely determined by the random errors in measured concentrations. The meteorological surface exchange parameters can be estimated sufficiently accurately (<20% uncertainty). At the grassland site, average surface resistances to deposition of 6(±8) and 13(±12) s m⁻¹ were calculated for wet and dry conditions, respectively. At the heathland site, a similar distinct difference between R_c values for wet and dry conditions was found. These values are 20(±21) and 70(±90) s m⁻¹, respectively. The yearly average dry deposition flux for SO₂ at the grassland site amounts to 585(±330) mol ha⁻¹ yr⁻¹, while at the heathland site the yearly average flux was 300(±270) mol ha⁻¹ yr⁻¹. The yearly average dry deposition velocity at 4 m height was 1.2(±0.3) cm s⁻¹ at the grassland site and 0.8(±0.4) cm s⁻¹ at the heathland site.     

冬小麦田O3气孔与非气孔沉降及风险评估

为了深入了解农田生态系统的O_3干沉降过程,并基于O_3通量(尤其是气孔O_3累积通量)指标进行风险评估,利用涡度相关系统对冬小麦田的O_3干沉降过程进行了连续动态观测,初步分析O_3浓度和总O_3通量的变化过程,着重探析气孔O_3沉降和非气孔O_3沉降的变化特征及其与主要气象因子的关系,并基于剂量指标(AOT40)和通量指标(DF_s06)分别推算出冬小麦的产量损失率.结果表明,观测期间(自2016年3月16日至5月30日)日平均O_3浓度(cO_3)为32.9 n L·L-1;白天(08:00~18:00)和夜间平均总O_3通量(F_(O3))分别为-7.6 nmol·(m~2·s)~(-1)和-3.1 nmol·(m~2·s)~(-1),日均F_(O3)为-5.1nmol·(m~2·s)~(-1).逐日平均气孔O_3通量(F_s)的变化范围为0~-5.1 nmol·(m~2·s)~(-1),日均F_s为-1.43 nmol·(m~2·s)~(-1).逐日平均非气孔O_3通量(F_(ns))的变化范围为-1.43~-10.31 nmol·(m~2·s)~(-1),日均F_(ns)为-3.66 nmol·(m~2·s)~(-1).较强的太阳辐射(SR)、较高的温度(T)和适度湿润的条件有利于冬小麦气孔沉降;较强的SR、适度的T和湿润条件是有利于冬小麦非气孔沉降.在整个观测期间,总O_3累积吸收通量(DF_(O3))、气孔O_3累积吸收通量(DF_s)和非气孔O_3累积吸收通量(DF_(ns))分别为31.58、9.99和21.59 mmol·m~(-2),总DF_s和总DF_(ns)分别占总DF_(O3)的32%和68%.通过剂量指标AOT40和通量指标DF_s06响应方程计算出的冬小麦产量损失率分别为11.58%~20.37%和20%~23.56%.     

Fluxes of nitric and nitrous oxides from agricultural soils in a cool temperate climate

Fluxes of NO and N₂O from sandy loam soils cropped with winter wheat and a clay loam soil under ryegrass, with and without the addition of NH₄NO₃ fertilizer, were measured using static and dynamic chamber methods. Nitric oxide fluxes ranged from −0.3 (deposition) to 6.9 (emission) ng NO-N m⁻² s⁻¹. The corresponding N₂O flux ranged from 0 to 91 (emission) ng N₂O-N m⁻² s⁻¹. The NO flux was temperature dependent. Activation energies ranged from 40 to 81 kJ mol⁻¹. Nitric oxide and N₂O fluxes increased linearly with soil available nitrogen (NH₄ + NO₃). Emissions of NO and N₂O were not detectable from unfertilized ryegrass plots. Instead, nitric oxide was absorbed by the soil and vegetation at a maximum rate of 0.31 ng NO-N m⁻² s⁻¹. The aeration state of the soil controlled the relative rates of NO and N₂O emission. Nitric oxide was the major gas emitted from well aerated soils, conditions that favour nitrification. The NO/N₂O emission ratio was >100 for the coarse-textured sandy loam soil and the clay loam soil only during low rainfall periods. Nitrous oxide was the major gas emitted from less aerated soils, conditions that allowed denitrification to occur. The NO/N₂O emission ratio was <0.001 for the clay loam soil when rainfall was high and soils were wet. Extrapolation to the U.K. situation showed that agricultural land may account for 2–6% of the total annual NO_x emission and for 16–64% of the total annual N₂O emission in the U.K.     

Modeling of SO2, Pb and Cd atmospheric deposition over a one-year period

Atmospheric deposition of SO₂, and fine particles of Pb and Cd are calculated over a one-year period in a 66 km² airshed with a segment-puff model. Emission variations, hourly mixing heights and meteorological values are considered to compute monthly averages of concentrations and deposition. Dry deposition is calculated by means of deposition velocities which are season- and land use-dependent. Wet deposition is determined using a washout coefficient. To assess the simulation performance, calculated SO₂ results from the combination between the deposition velocity, the windspeed and direction and the location and type of sources. As annual averages, results for dry plus wet deposition are computed to be 0.84 mg m⁻²d⁻¹ for sulfur, 4.15 μgm⁻²d⁻¹ for lead and 0.0013 μgm⁻²d⁻¹ for cadmium. A variation factor is derived from a sensitivity analysis. This factor amounts to 2.3−2.8 for the concentrations and 2.6−3.1 for the deposition, depending on the pollutant.     

Scavenging ratios and deposition of sulphur,nitrogen and chlorine species in eastern England

Measurements of wet deposited NH₄⁺, SO₄²⁻, NO₃⁻ and Cl⁻, as well as airborne concentrations of these species and gaseous HNO₃, HCl and NH₃, have been made at a site in eastern England. Scavenging ratios based solely upon aerosol-associated species and upon aerosol plus gaseous airborne species are presented and compared with literature values. It appears that HCl and HNO₃ have only a rather minor influence upon wet deposition at our site. Gaseous NH₃ influences ground-level air chemistry appreciably, but scavenging ratios for NH₄⁺ are low, even when based upon aerosol NH₄⁺ concentrations alone, presumably due to altitudinal gradients in this species. The problems inherent in interpretation of scavenging ratios are discussed. Deposition of nitrogen in various chemical forms is estimated from rainwater and air composition. If a transport-limited deposition velocity is assumed for ammonia gas, dry deposition of this species accounts for around 40% of total nitrogen deposition to the ground.     

The effect of wind velocity,air temperature and humidity on NH3 and SO2 transfer into bean leaves (phaseolus vulgaris L.)

The influence of wind velocity, air temperature and vapour pressure deficit of the air (VPD) on NH₃ and SO₂ transfer into bean leaves (Phaseolus vulgaris L.) was examined using a leaf chamber. The measurements suggested a transition in the properties of the leaf boundary layer at a wind velocity of 0.3–0.4 ms⁻¹ which corresponds to aRe_crit value of about 2000. At higher wind velocities the leaf boundary layer resistance (r_b) was 1.5–2 times lower than can be calculated from the theory. Nevertheless, the assessed relationships betweenr_b and wind velocity appeared to be similar to the theoretical derived relationship forr_b. The NH₃ flux and in particular the SO₂ flux into the leaf strongly increased at a VPD decline. The increase of the NH₃ flux could be attributed to an increase of the stomatal conductance (g_s). However, the increase of the SO₂ flux could only partly be explained by an increase ofg_s. An apparent additional uptake was also observed for the NH₃ uptake at a low temperature and VPD. The SO₂ flux was also influenced by air temperature which could be explained by a temperature effect ong_s. The results suggest that calculation of the NH₃ and SO₂ flux using data ofg_s gives a serious understimation of the real flux of these gases into leaves at a low temperature and VPD.     

Cloud chemistry measurements and estimates of acidic deposition on an above cloudbase coniferous forest

The wet, dry and cloud water deposition of acidic substances on the forest canopy are considered as major mechanisms for pollutant induced forest decline at high elevations. Direct cloud capture plays a predominant role of intercepting acidic substances in above cloud-base forests. We conducted a field study at Mt. Mitchell, North Carolina (35°44′05″N, 82°17′15″W; 2038 m MSL)—the highest peak in the eastern U.S.—during May–September 1986 and 1987 in order to analyze the chemistry of clouds in which the red spruce and Fraser fir stands stay immersed. It was found that Mt. Mitchell was exposed to cloud episodes 71% of summer days, the cloud immersion time being 28% for 1986 (a record drought summer in southeastern U.S.) and 41% for 1987. Sulfate, NO₃⁻, NH₄⁺ and H⁺ ions were found to be the major constituents of the cloud water, which was collected atop a 16.5 m tall meteorological tower situated among 6–7 m tall Fraser fir trees. The initiation of precipitation in clouds invariably diluted the cloud water acidity. The cloud water pH during short episodes (8 h duration or less), which resulted from the orographic lifting mechanisms, was substantially lower than that during long episodes, which were associated with meso-scale and synoptic-scale disturbances. Sulfate accounted for 65% acidity in cloud water, on the average, and contributed 2–3 times more than the NO₃⁻. Inferential micrometeorological models were used to determine deposition of SO₄²⁻ and NO₃⁻ on the forest canopy and the hydrological input due to direct cloud capture mechanism. The cloud water deposition ranged between 32 and 55 cm a⁻¹ in contrast to the bulk precipitation which was about 130 cm a⁻¹ as measured by an on-site NADP (National Atmospheric Deposition Program) collector. For S compounds, wet, dry and cloud water deposition accounted for 19%, 11% and 70%, respectively for 1986, and 16%, 8% and 76%, respectively for 1987. For N compounds, dry deposition contributed 35% and 23% for 1986 and 1987, respectively, whereas, cloud water deposition contributed 50% and 65% for 1986 and 1987, respectively. Our estimates are compared with the reported literature values for the other sites.     

In-cloud scavenging and deposition of sulfates and nitrates: Case studies and parameterization

Scavenging of sulfates and nitrates—two most common ions leading the cloudwater acidity—was investigated during field studies atop a site in Mt. Mitchell (35°44′05″N, 82°17′15″W) State Park where the highest peak (2038 m MSL) of the eastern U.S. is located. Experiments were conducted during the growing seasons (15 May–30 September) of 1986 and 1987 using an instrumented meteorological tower (16.5 m tall) and a passive cloudwater collector. A cloud episode that occurred on 12 October 1987, was also comprehensively investigated. Clouds were frequently observed in which the Fraser fir and red spruce stands stayed immersed 28% and 41% of the time during the 1986 and 1987 seasons, respectively. Rate of cloudwater deposition on the forest canopy was determined using an inferential cloud deposition model. It was found by analysing nine short duration (lasting 8 h or less) and 16 long duration cloud events that the ionic concentration (SO₄²⁻ and NO₃⁻) is inversely proportional to the rate (I_c) of cloudwater deposition (in mm h⁻¹) and can be expressed by the following relationship: [SO₄²⁻] = aI_c^−b or [NO₃⁻] = aI_c^−b. Theoretical arguments leading to these relationships are presented. The b values for predicting NO₃²⁻ concentration are found in the range of 0.14–1.24 (mean = 0.48) for short duration and 0.062–0.63 (mean = 0.27) for long duration cloud events, respectively. The corresponding b values for predicting NO₃⁻ concentrations are 0.19–1.16 (mean = 0.49) and 0.072–0.59 (mean = 0.27), respectively. When the b parameter was between 0.2 and 0.6, the correlation coefficients between measured and predicted ionic concentrations were found to exceed 0.7. The parameter a is shown to represent the maximum ionic flux for a given cloud event. The ratio of the a parameter for SO₄²⁻ to NO₃⁻ varied between 1.75 and 6.95, indicating that the SO₄²⁻ contributes to the total ionic concentration substantially more than the NO₃⁻ leading to the conclusion that the cloudwater acidity is primarily due to the presence of sulfuric acid which has been demonstrated to cause foliar injury and growth retardation in red spruce trees. The above parameterization is similar to the one that is frequently used to relate ionic concentration in precipitation to the rainfall rate. In order to understand physico-chemical processes leading to the proposed parameterization schemes, meteorological and chemical variables are comprehensively analysed for one short duration and two long duration cloud events. The concentrations of principal ions (SO₄²⁻, NO₃⁻, H⁺ and NH₄⁺) during the short duration cloud events were found to be much higher than those during the long duration ones, especially at colder temperatures. Such short cloud events have a potential of causing foliar narcosis in red spruce stands because of unusually acidic cloudwater to which these stands stay exposed intermittently during each growing season.     

吸收液对中空纤维膜接触器回收尿液中氨氮的影响

采用中空纤维膜接触器（Hollow Fiber Membrane Contactor, HFMC）回收尿液中的氨氮,系统研究了吸收液类型（H₃PO₄、H₂SO₄和HNO₃）对氨回收效能、水蒸气的跨膜通量和所获液体肥料的影响.结果表明,使用H₂SO₄作为吸收液时氨氮回收效能最优,其次是H₃PO₄和HNO₃.当采用H₂SO₄为吸收液时,氨氮回收率、氨跨膜通量和传质系数分别为84.49%±0.01%、22.92 g·m^-2·h^-1和2.37×10^-6 m·s^-1.HNO₃的挥发性使其从吸收液侧反向跨膜至料液侧,导致氨跨膜传质驱动力变小;此外,NH₃和HNO₃会在膜孔中反应并生成NH₄NO₃气溶胶,增加氨在膜孔中的传质阻力,导致氨氮的回收效能降低.对采用不同吸收液时膜两侧的水的活度差和理论水通量进行了计算,结果表明,随着氨氮的不断跨膜吸收,膜两侧的活度差和水通量逐渐增大,实验结束时水通量分别为7.44×10^-2 kg·m^-2·h^-1（H₃PO₄）、9.06×10^-2 kg·m^-2·h^-1（H₂SO₄）和2.00×10^-2 kg·m^-2·h^-1（HNO₃）.肥料组分分析表明,以H₂SO₄和HNO₃为吸收液可以获得仅含N素的单一液体肥料,以H₃PO₄作吸收液可获得N-P复合肥,（NH₄）₂HPO₄和NH₄H₂PO₄所占的比例分别为88.33%和11.67%.     

Atmospheric coarse particulate concentrations and dry deposition fluxes for ten metals in two urban environments

The atmospheric coarse particle concentrations of ten metals (Al, Ca, Cd, Cu, Fe, Mn, Ni, Pb, Si and Zn) were measured with the Noll Rotary Impactor (NRI) in the Los Angeles Basin (Claremont) California, and in Chicago, Illinois. The dry deposition fluxes were also measured for the ten elements at the Chicago site. An evaluation of the data demonstrates that the coarse particle mass could be divided into two categories: (1) material that was primarily of crustal origin (Al, Ca, Fe and Si) and (2) material that was primarily of anthropogenic origin (Cd, Cu, Mn, Ni, Pb and Zn). The mass of crustal material varied between 15 and 50% of the total coarse particle mass, while the mass of anthropogenic material was <1%. The dry deposition fluxes for the crustal material were between 20 (Al) and 200 (Si) ng m⁻² s⁻¹ while the fluxes for the anthropogenic material were between 1 and 7 ng m⁻¹ s⁻¹ for Cu, Mn, Pb and Zn. The cadmium (Cd) flux averaged 0.02 ng m⁻² s⁻¹.     

Laboratory measurements of sulfur dioxide deposition velocity on marble and dolomite stone surfaces

The deposition velocity of SO₂ on marble and dolomite stone surfaces in a humid atmosphere was measured as a function of time in the laboratory using continuous monitoring techniques. The deposition velocity of SO₂ on marble varied between 0.02 and 0.23 cm s⁻¹, and was generally observed to decrease with time. The deposition velocity of SO₂ on dolomite varied between 0.02 and 0.10 cm s⁻¹, and gradually increased over the first 2000 ppm-h of exposure. For both types of stones, the deposition velocity increased significantly when condensed moisture was observed on the stone surface. Chemical analysis of the stone samples indicated that the SO₂ deposited reacted with the stone materials to form gypsum (CaSO₄·2H₂O) on the marble surfaces and gypsum and epsomite (MgSO₄·7H₂O) on the dolomite surfaces.     

The spatial distribution and particle size of some inorganic nitrogen,sulphur and chlorine species over the North Sea

The use of filter packs and a cascade impactor during a series of research cruises in the southern area of the North Sea has yielded detailed spatial distribution patterns of aerosol concentrations, Cl⁻, NO₃⁻, SO₄²⁻¹ and NH₄⁺ and gaseous concentrations, HCl, HNO₃ and NH₃. The overall distribution of the atmospheric concentrations closely parallels published modelled results for metallic species. The chemical transformations of these aerosols and gases are investigated together with their interactions with the seasalt aerosol. Aerosol chloride loss is greatest in the more polluted areas, whilst concentrations products of NH₃ with HNO₃ and HCl appear insufficient to sustain the existence of NH₄NO₃ and NH₄Cl. Nitrate is associated predominantly with larger particles and appears to be present substantially as a surface coating on marine aerosol. The total dry deposition input for nitrogen species is calculated for the southern sector with extrapolation to the whole of the North Sea, using particle size weighted deposition velocities of 0.63 and 0.21 cm s⁻¹ for NO₃⁻¹ and NH₄⁺, respectively, and literature-derived values for the gaseous constituents. Finally the use of air-mass back trajectories illustrates the role of source regions in influencing the chemical composition of the North Sea atmosphere.     

Dry deposition of fine aerosol to a short grass surface

Soluble sulphate has been used as a marker for fine aerosols and dry deposition has been estimated using a profile technique. The effects of coarse particles were excluded from the measurements by passage of the sampled air through Nuclepore polycarbonate prefilters, resulting in a 2μm upper cut-off. A total of 99 separate experiments were conducted between June 1988 and June 1989 and 50 acceptable profiles remained after the application of a rigorous quality control procedure. The mean deposition velocity was found to be equal to 0.1 ± 0.03 (standard error) cm s⁻¹. There were no observed dependences of deposition velocity on either atmospheric stability or friction velocity within the range of conditions encountered.     

Apparent deposition velocity and compensation point of ammonia inferred from gradient measurements above and through alfalfa

Understanding the cycling of ammonia between croplands and the atmosphere is of importance to agriculturalists and atmospheric scientists. Flux densities of gaseous ammonia (NH₃), particulate ammonium (NH₄⁺), and total ammoniacal nitrogen (AN) were measured using an aerodynamic method above an alfalfa (Medicago sativa, L.) canopy between April and July 1981 at a rural location in central New York State. In air not influenced by local sources, NH₃ and NH₄⁺ averaged 1.5 and 3.0 ppb, respectively, at 1 m above the crop. Ambient NH₄⁺ varied consistently with synoptic air masses, being lowest (2.3 ppb) for NW and highest (6.4 ppb) for SW flows. Concentrations and gradients of both species were higher during periods of hay harvest. Gradients of NH₃ were much steeper than those of NH₄⁺ within the alfalfa canopy, but NH₄⁺ contributed appreciably (36% on average) to above-canopy AN gradients. Alfalfa's NH₃ compensation point was estimated by combining concentration and gradient data with transport resistances. Gaseous gradients indicated a compensation point of 2 ppb, lower than previously published estimates. Conversion of NH₃ to NH₄⁺ within the canopy air could have reduced NH₃ gradients and caused a low estimate of the compensation point. Acidic aerosols, by keeping NH₃ levels low, may compete with plants for NH₃. Future studies of ammonia exchange should distinguish between NH₃ and NH₄⁺ if flux densities are to be related to ambient conditions. Total AN level is a poor predictor of soil-plant-atmosphere ammonia exchange since high AN was frequently associated with low NH₃, and NH₃ is more surface reactive than NH₄⁺.     

Two options to explain the ammonia gap in The Netherlands

This paper addresses two hypothesis that try to explain the difference observed between the estimated NH₃ emission levels in The Netherlands and those indicated by atmospheric measurements, the so called ‘ammonia gap’: the role of SO₂ emissions regulating ambient NH₃ concentrations through co-deposition, and long-term NH₃ emissions after slurry injection. It was found that throughfall measurements of NH₄⁺ could not be used as indicator for changes in NH₃ emissions. The throughfall deposition of NH₄⁺ is in close equilibrium to SO₄²⁻ and NO₃⁻ and is thus regulated by the equilibrium of ambient NH₃ and NH₄⁺ in wet deposition and canopy water layers. When SO₂ emissions decrease, the amount of available SO₄²⁻ decreases, which imposes a limit on the deposition of (NH₄)₂SO₄. Long-term emissions of NH₃ after application of manure were monitored using a new technique, which continuously measures the concentration of NH₃ in a cross-section of the emission plume downwind of the source. The emissions could be registered for 3 weeks after application of manure. The results indicate that the long-term emissions only contribute 1–2% to the total emission level. Both the effect of SO₂ on the NH₃ deposition levels and the long-term emission fluxes are not enough to explain the observed ammonia gap. It seems that several counteracting effects, some of them emerging from the new emission reduction regulations, contribute to the ammonia gap. An integrated approach to abate ammonia emissions is, therefore, needed. The implementation and regulation of production ceilings for reactive nitrogen might be a good option.     

Aspects of wet,acidifying deposition in Arnhem: Source regions,correlations and trends (1984–1991)

A time series of wet deposition in Arnhem, the Netherlands, was analysed for the period 1984–1991. Precipitation was collected with four samplers on a daily basis. A comparative study by the Dutch National Precipitation Network showed significant biases for the observations of the National Network station due to longer exposure to dry deposition. Simultaneous operation of wet-only and bulk collectors demonstrated a concentration bias of about 10% for daily bulk sampling.Using a cluster analysis of backward trajectories, clear distinctions could be made between precipitation from continental and maritime origin. Event-to-event variations in deposition seemed to be determined largely by meteorological influences. As major anthropogenic source regions, the U.K., France, Belgium and the Netherlands itself were identified. The contribution of Dutch sources to wet acid deposition in Arnhem was estimated at 30–40%.Trends and seasonal variations were analysed with an advanced time-series model based on Kalman filtering. Similar seasonal variations were found for SO₄²⁻ and NH₄⁺. Also, seasonal variations in the concentrations of H⁺ and NO₃⁻ corresponded. Significant long-term changes in deposition and concentration were found for SO₄²⁻ (about −3% yr⁻¹) and H⁺ (about −9% yr⁻¹) only. The analysed trends were decreasing, but decreases were larger in the years 1984–1986 than in the following years. The relative decrease in the wet deposition of SO₄²⁻ was substantially smaller than decrease in dry-deposited SO₂ and SO₄²⁻.     

Kinetics of evaporation of ammonium chloride and ammonium nitrate aerosols

The evaporation rates of ammonium chloride and ammonium nitrate were measured by continuously and rapidly removing gaseous NH₃ and HNO₃ or HCl from aerosols in an annular denuder. The experiments gave the evaporation rates in terms of mass loss of chloride or nitrate which can be expressed conveniently as the rates of reduction of aerosol radius with time. Both dry aerosols (humidity 30–60% r.h.) and aqueous aerosols (humidity ca 97% r.h.) were studied. Dry aerosols evaporate at rates of −1.05 Å s⁻¹ for NH₄Cl and −0.45Å s⁻¹ for NH₄NO₃, while the evaporation rates of aqueous aerosols expressed as for equivalent dry particles are −4.52 Å s⁻¹ for NH₄Cl and −0.49 Å s⁻¹ for NH₄NO₃. The experimentally measured rates are independent of particle radius and remarkably low compared with those predicted from existing theories of aerosol evaporation, thus implying that there is an unknown kinetic constraint to the achievement of equilibrium at atmospheric temperature and pressures.     

On the interaction between equilibration processes and wet or dry deposition

Atmospheric equilibration processes between two phases with different deposition velocities have the potential to affect significantly the amount of total material deposited on the ground. The magnitude of the effects of the equilibration processes depends primarily on the ratio of the deposition velocities of the two phases, on the production/emission rate of the gas phase species, and on the initial distribution of species between the two phases. The deposition of a condensible species equilibrating between gas and aerosol phases can increase by as much as 20 times over that when equilibration processes are not present under appropriate conditions (very large aerosol particles, most of the material initially in the gas phase and high gas-phase production rate) or to decrease by as much as 15 times (very small aerosol particles, most of the material initially in the gas phase and high gas-phase production rate). In fog episodes, the deposition of a gaseous species with a Henry's Law constant between 10³ and 10⁶ M atm⁻¹ (e.g. SO² for pH between 4.5 and 7, H₂O₂, HCHO etc) can be enhanced by as much as a factor of 3 because of its transfer to the aqueous phase. For the NH₃HNO₃NH₄NO₃ system the total deposition can be reduced by as much as a factor of 3 for typical conditions in a polluted atmosphere and small initial concentration of aerosol NH₄NO₃ with NH₃ initially dominating HNO₃ in the gas phase. If an operator splitting scheme is used in a mathematical both equilibration and removal processes should be included in the same operator or very small operator time steps (typically less than 1 min) will be necessary.     

Deposition and forest canopy interactions of airborne sulfur: Results from the integrated forest study

The Integrated Forest Study (IFS) was a long-term research project designed to determine the effects of atmospheric deposition on forest nutrient cycles. Concentrations and fluxes of airborne sulfur compounds were determined for several years at the 13 IFS research forests in North America and Europe using a standard set of protocols. Annual mean air concentrations of sulfur ranged from ∼1.5 to 8 μgSm⁻³ and were generally dominated by SO₂ (∼60% of total sulfur on the average). Atmospheric deposition of sulfate at these forests was highest at the high elevation (∼ 1000–2000 eq ha⁻¹yr⁻¹) and at the southeastern U.S. sites (∼800–1000 eq ha⁻¹yr⁻¹), and lowest in the Pacific northwest (∼300 eq ha⁻¹yr⁻¹). Cloud water contributed significantly to the sulfur flux at the mountain sites (45–50%), and dry deposition was comparable to wet at the drier southeastern sites (>40% of total). Deposited sulfur appeared to behave more or less conservatively in these canopies, showing little net uptake (ofSO₂) and minor foliar leaching (of soil-derived, internal SO₄²⁻) relative to the total atmospheric flux. The estimated fluxes in total deposition were generally within 15% of the measured fluxes in throughfall plus stemflow, indicating that useful estimates of total atmospheric deposition of sulfur can be derived from measurements of throughfall.     

Estimates of ion sources in deciduous and coniferous throughfall

Estimates of external and internal sources of ions in net througfall deposition were derived for a deciduous and coniferous canopy by use of multiple regression. The external source component appears to be dominated by dry deposition of Ca²⁺, SO₂ and NO₃⁻ during dormant and growing seasons for the two canopy types. Increases in the leaching rates of K⁺ and Mg²⁺ during the growing season reflect the presence of leaves in the deciduous canopy and increased physiological activity in both canopies. Internal leaching rates for SO₄²⁻ doubled during the growing season presumably caused by increased physiological activity and uptake of SO₂ through stomates. Net deposition of SO₄²⁻ in throughfall during the growing season appears highly dependent on stomatal uptake of SO₂. Estimates of SO₂ deposition velocities were 0.06 cm s⁻¹ and 0.13 cm s⁻¹ for the deciduous and coniferous canopies, respectively, during the dormant seasons, and 0.30 cm s⁻¹ and 0.43 cm s⁻¹ for the deciduous and coniferous canopies, respectively, during the growing season. For the ions of major interest with respect to ecosystem effects, namely H⁺, NO₃⁻ and SO₄²⁻, precipitation inputs generally outweighed estimates of dry deposition input. However, net throughfall deposition of NO₃⁻ and SO₄²⁻ accounted for 20–47 and 34–50 per cent, respectively, of total deposition of those ions. Error estimates of ion sources were at least 50–100 per cent and the method is subject to several assumptions and limitations.