Greenhouse effect of NOX

Through various processes the nitrogen oxides (NO_X) interact with trace gases in the troposphere and stratosphere which do absorb in the spectral range relevant to the greenhouse effect (infrared wavelengths). The net effect is an enhancement of the greenhouse effect. The catalytic role of NO_X in the production of tropospheric ozone provides the most prominent contribution. The global waming potential is estimated as GWP (NO_X = 30 – 33 and 7 – 10 for the respective time horizons of 20 and 100 years, and is thereby comparable to that of methane. NO_X emissions in rural areas of anthropogenically influenced regions, or those in the vicinity of the txopopause caused by air traffic, cause the greenhouse effectivity to be substantially more intense. We estimate an additional 5–23 % for Germany’s contribution to the anthropogenic greenhouse effect as a result of the indirect greenhouse effects stemming from NO_X. Furthermore, a small and still inaccurately defined amount of the deposited NO_X which has primarily been converted into nitrates is again released from the soil into the atmosphere in the form of the long-lived greenhouse gas nitrous oxide (N₂O). Thus, anthropogenically induced NO_X emissions contribute to enhanced greenhouse effect and to stratospheric ozone depletion in the time scale of more than a century.     

Secondary air pollutants

The study has been performed in a supposedly clean-air region of a Northern Finnish forest with a homogeneous stand of Scots pine. Stomatal epicuticular wax layer erosion is described using a classification system of five erosion stages. The percentage of stomatal wax within each erosion stage is calculated and the results are treated statistically, which makes the morphological study of the needle surface semi-quantitative. Severe wax degradation has already been found in the current year, increasing with the age of the needles. In this area, the wax layer erosion is correlated with secondary air pollutants, as analyses have shown high trichloroacetate (TCA) levels in needles from the same trees. The wax layer analyses are in accordance with earlier findings which have demonstrated differences in tolerance to TCA.     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Diffusive sampling of methyl isocyanate using 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ) as derivatizing agent

A diffusive sampling method for the determination of methyl isocyanate (MIC) in air is introduced. MIC is collected using a glass fiber filter impregnated with 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ). The urea derivative formed is desorbed from the filter with acetonitrile and analyzed by means of high-performance liquid chromatography (HPLC) using fluorescence detection (FLD) with lambdaex = 471 nm and lambdaex = 540 nm. Additionally, a method was developed using tandem mass spectrometric (MS-MS) detection, which was performed as selected reaction monitoring (SRM) on the transition [MIC-NBDPZ + H]+ (m/z 307) to [NBDPZ + H]+ (m/z 250). The diffusive sampler was tested with MIC concentrations between 1 and 35 microg m(-3). The sampling periods varied from 15 min to 8 h, and the relative humidity (RH) was set from 20% up to 80%. The sampling rate for all 15 min experiments was determined to be 15.0 mL min(-1) (using HPLC-FLD) with a relative standard deviation of 9.9% for 56 experiments. At 80% RH, only 15 min sampling gave acceptable results. Further experiments revealed that humidity did not affect the MIC derivative but the reagent on the filter prior to and during sampling. The sampling rate for all experiments (including long term sampling) performed at 20% RH was found to be 15.0 mL min(-1) with a relative standard deviation of 6.3% (N = 42). The limit of quantification was 3 microg m(-3) (LC-MS-MS: 1.3 microg m(-3)) for 15 min sampling periods and 0.2 microg m(-3) (LC-MS-MS: 0.15 microg m(-3)) for 8 h sampling runs applying fluorescence detection.     

Biochemical and Physiological Detection of Sulfur Dioxide Injury to Pea Plants (Pisum sativum)

Biochemical and physiological experiments were conducted on pea plants (Pisum sativum) continuously exposed in growth chambers to SO₂ gas for 18 days. S0₂ gas concentrations were 0.1, 0.15, and 0.25 ppm. In plants exposed to 0.1 and 0.15 ppm it was clearly demonstrated that there was a greater accumulation of inorganic sulfur, a reduced buffer capacity of the cells relative to H-ions, and a stimulation of glutamate dehydrogenase activity. The only macroscopic symptom seen was slight chlorosis of the older leaves. There was only a slight decrease in fresh and dry weights of these plants compared to the control plants whereas in the group of plants exposed to 0.25 ppm SO₂ foliage necrosis was considerable. In addition, there was a marked reduction in the fresh and dry weights of the latter plants. However, the relationship among accumulated inorganic sulfur, reduced buffer capacity, and increased glutamate dehydrogenase activity as seen for the lower S0₂ concentrations was close. Accordingly, if might be possible to use these three parameters to diagnose S0₂ injury before any significant symptoms appear. In the case of severe SO₂ injury there was a marked increase in glutamine and ammonia concentrations suggesting that these factors in addition to the above could be used in diagnosing severe SO₂ injury. There was no significant difference between plants treated with 0.1 or 0.15 ppm SO₂ and control plants in the contents of K, Ca, P, and N fractions. Therefore, these factors would not be useful in the early detection of SO₂ injury.     

Validation of spectral gas radiation models under oxyfuel conditions. Part A: Gas cell experiments

Combustion of hydrocarbon fuels with pure oxygen results in a different flue gas composition as combustion with air. Standard CFD spectral gas radiation models for air combustion are out of their validity range. The series of three articles provides a common spectral basis for the validation of new developed models. In part A of the series gas cell transmissivity spectra in the spectral range of 2.4–5.4 μm of water vapor and carbon dioxide in the temperature range from 727 to 1500 ° C and at different concentrations were compared at a nominal resolution of 32 cm^?1 to line-by-line models from different databases, two statistical-narrow-band models and the exponential wide band model. The two statistical-narrow-band models EM2C and RADCAL showed a good agreement with a maximal band transmissivity deviation of 3%. The exponential-wide-band model showed a deviation of 6%. The new line-by-line database HITEMP2010 had the lowest band transmissivity deviation of 2.2% and was recommended as a reference model for the validation of simplified CFD models.