SMOG chamber studies of NOx chemistry in power plant plumes

Smog chamber simulations have been conducted in a 17m³ irradiation chamber with the purpose of identifying the effects of five independent variables on the transformation rates and product distributions of nitrogen and sulfur species in dilute power plant plumes. The study was designed to simulate the conditions in a plume starting at the point where half the NO has been oxidized to NO₂, where the plume will have been extensively diluted with background air containing hydrocarbons and ozone. The variables studied include: (1) plume hydrocarbon/NO_x ratio; (2) composition of organics in the diluting air; (3) NO_x/SO₂ ratio; (4) relative humidity; (5) presence of pre-existing acid sulfate aerosol. The starting concentrations and ratios of plume constituents were based on actual plume data.The results of the study are presented in terms of the impact of the independent variables on the extent of NO_x conversion to products, the rate of NO_x and SO₂ transformation to products and the relative distribution of gaseous and aerosol nitrate products. Briefly, the NO_x transformation rate is found to be dependent on hydrocarbon composition, hydrocarbon/NO_x ratio and relative humidity. The rates are essentially independent of SO₂ concentration or the presence of pre-existing H₂SO₄ aerosol surface. The SO₂ transformation rate appears to be independent of all five independent variables. The distribution of the nitrate products, nitric acid, peroxyacetyl nitrate and paniculate nitrate is a function of HC composition, HC/NO_x ratio and irradiation time. The effects of HC composition and HC/NO_x ratio decrease at the longer irradiation times characteristic of transport conditions.     

Physico-chemical speciation and transformation reactions of particulate atmospheric nitrogen and sulphur compounds

Using X-ray powder diffraction it is possible to identify a number of discrete compounds of nitrogen and sulphur in atmospheric aerosols. The compounds observed include ammonia neutralization products of airborne acids, including mixed ammonium nitrate-sulphate salts. Products of hydrogen halide displacement by HNO₃ and H₂SO₄ are identified both from size-differentiated ion balance studies and X-ray diffraction. A number of mixed metal-ammonium sulphate salts are attributed to reactions of ammonium sulphate subsequent to aerosol coagulation processes.     

Treating uncertainty in models of the atmospheric chemistry of nitrogen compounds

The paper presents a highly simplified model of the long-range transport and deposition of nitric oxide, nitrogen dioxide, gaseous nitric acid and nitrate aerosol over NW Europe. A ‘constant drizzle’ representation of wet removal of gaseous nitric acid and nitrate aerosol is developed in addition to the representation of dry deposition using appropriate deposition velocities. An analysis of the sensitivity of dry and wet deposition rates of oxidized nitrogen species at a remote, receptor site to the individual model parameters is described. This analysis is extended using latin hypercube sampling to an evaluation of the uncertainties in modelled dry and wet deposition and the contribution played by each model input parameter.     

The effects of atmospheric nitrogen deposition on the soil chemistry of coniferous forests in The Netherlands

Nitrogen fluxes, particularly those of ammonium, are extremely high in Dutch forests. In soils exposed to high ammonium deposition, acidification, eutrophication or a combination of both processes may occur. In addition to the amounts of ammonium deposited, the rate of soil nitrification determines which process takes place. A nation-wide investigation, in which three coniferous tree species were involved, was carried out to study the relation between deposition fluxes, measured by means of throughfall and bulk samplers, and the chemical composition of the soil. The ammonium deposition accounted directly for the high ammonium content and the high ammonium/cation ratios in the soil. In the top layer of most of the forest soils which were investigated nitrification rates were low. In these stands ammonium/cation ratios in the soil often reflected ammonium/cation ratios in throughfall water. Even in soils with relatively high nitrification rates, ammonium concentrations exceeded those of nitrate in the top layer of the mineral soil, indicating that ammonium deposition was more important than nitrification rate in determining the predominant form of nitrogen.     

Effects of reduced nitrogen and sulphur deposition on the water chemistry of moorland pools

To assess changes as a result of reduced acidifying deposition, water chemistry data from 68 Dutch moorland pools were collected during the periods 1983-1984 and 2000-2006. Partial recovery was observed: nitrate- and ammonium-N, sulphur and aluminium concentrations decreased, while pH and alkalinity increased. Calcium and magnesium concentrations decreased. These trends were supported by long term monitoring data (1978-2006) of four pools. Increased pH correlated with increases in ortho-phosphate and turbidity, the latter due to stronger coloration by organic acids. Increased ortho-phosphate and turbidity are probably the result of stronger decomposition of organic sediments due to decreased acidification and may hamper full recovery of moorland pool communities. In addition to meeting emission targets for NO_x, NH_x and SO_x, restoration measures are still required to facilitate and accelerate recovery of acidified moorland pools.     

Factors influencing ozone chemistry in subsonic aircraft plumes

This study investigates several factors that could influence ozone chemistry occurring in subsonic aircraft plumes in the upper troposphere. The study focuses on uncertainties in gas-phase rate parameters, but also examines the influence of selected heterogeneous reactions, the rate of expansion of the plume, ambient and initial plume concentrations, and the time of emissions. Monte Carlo analysis with Latin hypercube sampling was applied to an expanding box model of an aircraft plume, in order to estimate the sensitivities of O₃ perturbations (ΔO₃) to uncertainties in rate constants in the RADM2 chemical mechanism. The resulting coefficient of variation in ΔO₃ at the end of a 36 h simulation was about 50%. Influential uncertainties in gas-phase rate parameters include those for photolysis of NO₂ and HCHO, O₃+NO, HO₂+NO, and formation of PAN and HNO₃. With high background concentrations of non-methane hydrocarbons, uncertainties in rate parameters of reactions involving peroxy radicals from ethene and propene oxidation were also influential. The coefficient of variation for ΔO₃ due to uncertainties in emission indices of NO_x, CO, and organic compounds was less than 15%. The effects of the heterogeneous reaction of N₂O₅ leading to HNO₃ formation, and hypothesized reactions of HNO₃ and NO₂ on soot, were also investigated. The results suggest that the latter two reactions could be influential for ΔO₃ if published estimates of reaction probabilities and high estimates of soot concentrations in plumes are realistic.     

Deposition of sulphur,nitrogen and acidity in precipitation over Ireland: chemistry,spatial distribution and long-term trends

The chemical composition of pollutant species in precipitation sampled daily or weekly at 10 sites in Ireland for the five-year period, 1994–1998, is presented. Sea salts accounted for 81% of the total ionic concentration. Approximately 50% of the SO₄²⁻ in precipitation was from sea-salt sources. The proportion of sea salts in precipitation decreased sharply eastwards. In contrast, the concentration of NO₃⁻ and the proportion of non-sea-salt SO₄²⁻ increased eastwards reflecting the closer proximity to major emission sources. The mean (mol_c) ratio of SO₄²⁻:NO₃⁻ was 1.6 for all sites, indicating that SO₄²⁻ was the major acid anion.The spatial correlation between SO₄²⁻, NO₃⁻ and NH₄⁺ concentrations in precipitation was statistically significant. The regional trend in NO₃⁻ concentration was best described by linear regression against easting. SO₄²⁻ concentration followed a similar pattern. However, the regression was improved by inclusion of elevation. Inclusion of northing in the regression did not significantly improve any of the relationships except for NH₄⁺, indicating a significant increase in concentrations from northwest to southeast.The spatial distribution of deposition fluxes showed similar gradients increasing from west and southwest to east and northeast. However, the pattern of deposition shows the influence of precipitation volume in determining the overall input. Mean depositions of sulphur and nitrogen in precipitation were ≈30 ktonnes S yr⁻¹ and 48 ktonnes N yr⁻¹ over the five-year period, 1994–1998, for Ireland.Least-squares linear regression analysis indicated a slight decreasing trend in precipitation concentrations for SO₄²⁻ (20%), NO₃⁻ (13%) and H⁺ (24%) and a slight increasing trend for NH₄⁺ (15%), over the period 1991–1998.     

The chemistry of atmospheric mercury: a review

The atmosphere is an important transient reservoir of mercury. In addition to its great capacity, the chemical processes transforming mercury between the elemental and divalent states strongly influence the transport characteristics and deposition rate of this toxic metal back to the ground. Modeling efforts to assess global cycling of mercury require an in-depth knowledge of atmospheric mercury chemistry. This review article provides selected physical and chemical properties of atmospheric mercury, and discusses the identified mercury transformation pathways mediated by ozone, S(IV), hydroperoxyl radical, hydroxyl radical, chlorine, nitrate radical and photolysis of Hg(II) complexes. Special attention is paid to the kinetics and mechanisms of the reactions interconverting mercury between elemental and divalent states. The significance and implications of each transformation pathway under atmospheric conditions are addressed. Future research areas that must be pursued to better understand the fate and transformation of mercury in the atmosphere are also projected.     

A simple model which predicts some non-linear features between atmospheric sulphur and sulphur emissions

This paper develops a simple model and suggests a plausible chemico-physical mechanism for a non-linear response between atmospheric sulphur and sulphur emissions. It contains simplified representations of transport, deposition and conversion processes and uses a proxy in-cloud oxidant-limited reaction along a pathway connecting an emission source with a receptor site. Individual pathway responses to emissions show linear behaviour above a threshold. However, by averaging the values of SO2 at the receptor site from different pathways a continuous non-linear relationship is obtained. As emissions reduce, distant emission sources become less significant contributors of sulphur dioxide at a receptor site but their emissions are still counted in an emission inventory, leading to an apparent non-linearity. Sulphate is always found to contribute a signal to the receptor site total. This model goes someway to explaining a proposed 'crossover' between observed proportions of wet and dry deposited sulphur in the UK as emissions have been reduced.     

The importance of atmospheric ozone and hydrogen peroxide in oxidising sulphur dioxide in cloud and rainwater

The process by which sulphur dioxide is oxidised in atmospheric droplets has been studied in laboratory experiments designed to collect a large amount of chemical data pertinent to the atmospheric situation. Thus the oxidation of sodium sulphite solutions by oxygen, ozone and hydrogen peroxide has been studied at different pH's and temperatures. In all cases the reaction is first order with respect to sulphite ion but the order with respect to oxidant differs. For oxygen the order is zero whereas the order for ozone and hydrogen peroxide is one. Varying the hydrogen ion concentration has little effect on the oxygen reaction rate between pH 6 and 9; the ozone reaction rate is inversely proportional to the square root of the hydrogen ion concentration and the hydrogen peroxide rate is almost directly proportional to the hydrogen ion concentration. These last two observations are very important since in the case of ozone it indicates that the reaction proceeds via a free radical mechanism involving hydroxyl radicals and in the case of hydrogen peroxide it is the only oxidation process of sodium sulphite so far investigated that shows a positive response to the presence of hydrogen ions.The experimental data was used to calculate the rate of sulphate formation in water droplets under atmospheric conditions for each of the three oxidants. If it is assumed that the ozone and hydrogen peroxide gas phase concentrations are initially 50 parts in 10⁹ and 1 part in 10⁹ by volume respectively, then the rates of sulphate formation are equal in cloud water at pH 5.8. Above this pH the ozone reaction is faster and below it the hydrogen peroxide reaction is faster due to the positive catalysis by hydrogen ions; the oxygen rate is unimportant by comparison at all pH's below 7. The rate of hydrogen peroxide reaction is such that substantial amounts of sulphate can still be formed rapidly in water droplets at pH values from 3 to 5, and thus this process will be very important in creating acidity in rainwater.     

The importance of atmospheric ozone and hydrogen peroxide in oxidising sulphur dioxide in cloud and rainwater

The process by which sulphur dioxide is oxidised in atmospheric droplets has been studied in laboratory experiments designed to collect a large amount of chemical data pertinent to the atmospheric situation. Thus the oxidation of sodium sulphite solutions by oxygen, ozone and hydrogen peroxide has been studied at different pH's and temperatures. In all cases the reaction is first order with respect to sulphite ion but the order with respect to oxidant differs. For oxygen the order is zero whereas the order for ozone and hydrogen peroxide is one. Varying the hydrogen ion concentration has little effect on the oxygen reaction rate between pH 6 and 9; the ozone reaction rate is inversely proportional to the square root of the hydrogen ion concentration and the hydrogen peroxide rate is almost directly proportional to the hydrogen ion concentration. These last two observations are very important since in the case of ozone it indicates that the reaction proceeds via a free radical mechanism involving hydroxyl radicals and in the case of hydrogen peroxide it is the only oxidation process of sodium sulphite so far investigated that shows a positive response to the presence of hydrogen ions.The experimental data was used to calculate the rate of sulphate formation in water droplets under atmospheric conditions for each of the three oxidants. If it is assumed that the ozone and hydrogen peroxide gas phase concentrations are initially 50 parts in 10⁹ and 1 part in 10⁹ by volume respectively, then the rates of sulphate formation are equal in cloud water at pH 5.8. Above this pH the ozone reaction is faster and below it the hydrogen peroxide reaction is faster due to the positive catalysis by hydrogen ions; the oxygen rate is unimportant by comparison at all pH's below 7. The rate of hydrogen peroxide reaction is such that substantial amounts of sulphate can still be formed rapidly in water droplets at pH values from 3 to 5, and thus this process will be very important in creating acidity in rainwater.     

Visibility in London and the long distance transport of atmospheric sulphur

The long distance transport of air pollutants and summer visibility in London is related to sulphate concentration and wind direction. The results suggest that a non-linear, approximately inverse relationship exists between visibility and aerosol sulphate concentration. The worst mean visibility (6.4km) and the highest daily mean sulphate concentration (16.0 μg m⁻³) both occur in airflows between east and south. The most likely source of the sulphate on these occasions would be emissions on the continental mainland.     

Tracing sources of atmospheric sulphur using epiphytic lichens

The overall objective of this work was to measure the spatial variation of sulphur isotopic composition of lichens across the island of Newfoundland in order to assess the degree to which the atmosphere is being affected by long-range transport of anthropogenic sulphur from eastern North America, and/or local pollution sources. A contour map (based on over 80 composite samples of the lichen Alectoria sarmentosa) illustrates the spatial distribution of sulphur isotopic composition of the Newfoundland atmosphere. It shows a gradient of delta(34)S of sulphur in lichen, decreasing from the coast to the interior of the island. It also shows local anomalies corresponding to the city of St. John's, the Come-By-Chance Oil Refinery, mining areas and fossil-fuel powered pulp and paper mills in central and western Newfoundland. The study strongly suggests that the isotopic composition of sulphur in the Newfoundland atmosphere is influenced more by the ocean (sea salt sulphate) and local anthropogenic activities in the province, than by long-range transport of continental North American sulphate.     

Night-time atmospheric chemistry of methacrylates

Background, aim, and scope  

Methacrylates are α, β-unsaturated esters that are widely used in the polymer plastics and resins production. Kinetic information of NO₃ radical reactions is especially scarce and a good understanding of all the atmospheric oxidation processes of these compounds is necessary in order to determine lifetimes in the atmosphere and to evaluate the impact of these reactions on the formation of ozone and other photooxidants.     

Lichens and atmospheric sulphur: what stable isotopes reveal

Stable isotopes expand the range of applications for lichen biomonitoring of atmospheric sulphur.     

The effects of atmospheric nitrogen deposition and soil chemistry on the nutritional status of Pseudotsuga menziesii, Pinus nigra and Pinus sylvestris

The ammonium content and the base cation content, expressed relative to ammonium, are enhanced in the soil of Dutch forests, due to the extremely high deposition of ammonium to the forest floor. A nation-wide investigation was carried out to establish whether and how these changed nitrogen fluxes in deposition and soil affect the nutritional status of coniferous trees. The chemical composition of needles of Douglas fir, Scots pine and Corsican pine showed a regional trend similar to that of deposition and soil solution. Particularly nutrients, expressed relative to nitrogen, decreased from North to South. Of the macronutrients phosphorus was most often deficient and therefore probably limiting in the Douglas fir stands. Many pine trees suffered from relative magnesium shortages. In all stands, magnesium and, in Douglas stands, also phosphorus contents of the needles were negatively correlated with ammonium and ammonium/cation ratios in deposition. However, in contrast to pine trees, nutrient contents in needles of Douglas fir showed correlation with nitrate rather than with ammonium in the soil solution. Correlation analyses indicate that nitrogen fluxes in the soil, indirectly affect the nutritional status of coniferous trees.     

Ecosystem effects of atmospheric deposition of nitrogen in The Netherlands

Atmospheric deposition of inorganic N, mainly ammonium volatilized from manure produced in intensive stockbreeding, on sensitive terrestrial and aquatic ecosystems in The Netherlands is in the order of 40 to 80 kg ha(-1) year(-1). Proven effects of this deposition are (i) eutrophication with N, leading to floristic changes (ii) acidification of base-poor sandy soils and of moorland pools, leading to higher concentrations of dissolved, potentially toxic metals such as Al3+, and (iii) increased levels of nitrate in groundwater below woodlands. In acid forest soils, but not in soils under heathland, nitrification and leaching of nitrate is common. However, in very poor sandy forest soils and at very high ammonium inputs, nitrification may be too slow to prevent the development of high concentrations of ammonium. Both excessive acidification and excessive levels of ammonium probably play an important role in the general forest decline, which is most severe in the southern and central parts of the country, where ammonium inputs are highest.     

Competitive diesel engine emissions of sulphur and nitrogen species

NO_x, nitrate and sulphate emissions from a typical European passenger car diesel engine have been measured testing eight different fuels under five steady operating conditions (reproducing modes of the European transient urban/extraurban certification cycle). It is confirmed that nitrogen species compete with sulphur compounds to be adsorbed by diesel particulate matter (DPM) before being emitted into the atmosphere. This competition is found to increase with engine load, and is explained on the basis of the different specific surface and adsorption capacity of soot particles under different operating modes. When a high specific surface is available, as occurs in low load modes, both nitrates and sulphates are adsorbed by soot particles. On the contrary when a small surface is accessible, like in high load modes, sulphates are selectively adsorbed. This is specially important since sulphates are responsible for hydrocarbon retention in DPM due to the scrubbing effect.