Ozone and increased nitrogen supply effects on the yield and nutritive quality of Trifolium subterraneum

The influence of ambient ozone (O₃) concentrations and nitrogen (N) fertilization, singly and in combination, on the growth and nutritive quality of Trifolium subterraneum was assessed. This is an important O₃-sensitive species of great pastoral value in Mediterranean areas. Plant material was enclosed in open-top chambers (OTCs). Three O₃ levels were established: Filtered air with O₃ concentrations below 15 ppb (CFA), non-filtered air with O₃ concentrations in the range of ambient levels (NFA), and non-filtered air supplemented with 40 ppb O₃ over ambient levels (NFA+). Similarly, three N levels were defined: 5, 15 and 30 kg ha⁻¹. The increase in O₃ exposure induced a reduction of the clover aerial green biomass and an increase of senescent biomass. Ozone effects were more adverse in the root system, inducing an impairment of the aerial/subterranean biomass ratio. Compared with the CFA treatment, nutritive quality of aerial biomass was 10 and 20% lower for NFA and NFA+ treatments, respectively, due to increased concentrations of acid detergent fiber, neutral detergent fiber and lignin. The latter effect appears to be related to senescence acceleration. The increment in N supplementation enhanced the increase of ADF concentrations in those plants simultaneously exposed to ambient and above-ambient O₃ concentrations, and reduced the incremental rate of foliar senescence induced by the pollutant.     

Contrasting effects of ozone under different water supplies in two Mediterranean tree species

The effects of ozone (O₃) exposure under different water availabilities were studied in two Mediterranean tree species: Quercus ilex and Ceratonia siliqua. Plants were exposed to different O₃ concentrations in open top chambers (charcoal-filtered air (CF), non-filtered air (NF)) and non-filtered air plus 40 ppb_v of O₃ ((7:00–17:00 solar time) (NF+)) during 2 years, and to different water regimes (IR, sample irrigation, and WS, reduced water dose to 50%) through the last of those 2 years. AOT40 in the NF+ treatment was 59265 ppb_v h (from March 1999 to August 1999) while in the NF treatment, the AOT40 was 6727 ppb_v h for the same period. AOT40 was always 0 in the CF treatment. WS plants presented lower stomatal conductances and net photosynthetic rates, and higher foliar N concentrations than IR plants in both species. The irrigation treatment did not change the response trends to ozone in Q. ilex, the most sensitive species to O₃ ambient concentrations, but it changed those of C. siliqua, the least sensitive species, since its ozone-fumigated WS plants did not decrease their net photosynthetic rates nor their biomass accumulation as it happened to its ozone-fumigated IR plants. These results show interspecific variations in O₃ sensitivity under different water availabilities.     

Response of methane emission to invasion of Spartina alterniflora and exogenous N deposition in the coastal salt marsh

Spartina alterniflora exhibits great invading potential in the coastal marsh ecosystems. Also, nitrogen (N) deposition shows an apparent increase in the east of China. To evaluate CH₄ emissions in the coastal marsh as affected by the invasion of S. alterniflora and N deposition, we measured CH₄ emission from brackish marsh mesocosms vegetated with S. alterniflora and a native plant, Suaeda salsa, and fertilized with exogenous N at the rates of 0 and 2.7 g N m^?2, respectively. Dissolved porewater CH₄ concentration and redox potentials in soils as well as aboveground biomass and stem density of plants were also monitored. The averaged rate of CH₄ emission during the growing season in the S. alterniflora and S. salsa mesocosms without N application was 0.88 and 0.54 mg CH₄ m^?2 h^?1, respectively, suggesting that S. alterniflora plants significantly increased CH₄ emission mainly because of higher plant biomass rather than stem density compared to S. salsa, which delivered more substrates to the soil for methanogenesis. Exogenous N input dramatically stimulated CH₄ emission by 71.7% in the S. alterniflora mesocosm. This increase was attributable to enhancement in biomass and particularly stem density of S. alterniflora driven by N application, which transported greater photosynthesis products than oxygen into soils for CH₄ production and provided more pathways for CH₄ emission. In contrast, there was no significant effect of N fertilization on CH₄ emission in the S. salsa mesocosm. Although N fertilization significantly stimulated CH₄ production by increasing S. salsa biomass, no significant increase in stem density was observed. This fact, along with the low gas transport capacity of S. salsa, failed to efficiently transport CH₄ from wetlands into the atmosphere. Thus we argue that the stimulatory or inhibitory effect of N fertilization on CH₄ emission from wetlands might depend on the gas transport capacity of plants and their relative contribution to substrates for CH₄ production and oxygen for CH₄ oxidation in soil.     

Surface ozone-temperature relationships in the eastern US: A monthly climatology for evaluating chemistry-climate models

We use long-term, coincident O₃ and temperature measurements at the regionally representative US Environmental Protection Agency Clean Air Status and Trends Network (CASTNet) over the eastern US from 1988 through 2009 to characterize the surface O₃ response to year-to-year fluctuations in weather, for the purpose of evaluating global chemistry-climate models. We first produce a monthly climatology for each site over all available years, defined as the slope of the best-fit line (m_O3-T) between monthly average values of maximum daily 8-hour average (MDA8) O₃ and monthly average values of daily maximum surface temperature (T_max). Applying two distinct statistical approaches to aggregate the site-specific measurements to the regional scale, we find that summer time m_O3-T is 3–6 ppb K^?1 (r = 0.5–0.8) over the Northeast, 3–4 ppb K^?1 (r = 0.5–0.9) over the Great Lakes, and 3–6 ppb K^?1 (r = 0.2–0.8) over the Mid-Atlantic. The Geophysical Fluid Dynamics Laboratory (GFDL) Atmospheric Model version 3 (AM3) global chemistry-climate model generally captures the seasonal variations in correlation coefficients and m_O3-T despite biases in both monthly mean summertime MDA8 O₃ (up to +10 to +30 ppb) and daily T_max (up to +5 K) over the eastern US. During summer, GFDL AM3 reproduces m_O3-T over the Northeast (m_O3-T = 2–6 ppb K^?1; r = 0.6–0.9), but underestimates m_O3-T by 4 ppb K^?1 over the Mid-Atlantic, in part due to excessively warm temperatures above which O₃ production saturates in the model. Combining T_max biases in GFDL AM3 with an observation-based m_O3-T estimate of 3 ppb K^?1implies that temperature biases could explain up to 5–15 ppb of the MDA8 O₃ bias in August and September though correcting for excessively cool temperatures would worsen the O₃ bias in June. We underscore the need for long-term, coincident measurements of air pollution and meteorological variables to develop process-level constraints for evaluating chemistry-climate models used to project air quality responses to climate change.     

Concentration-dependent NH3 deposition processes for moorland plant species with and without stomata

Currently, in operational modelling of NH₃ deposition a fixed value of canopy resistance (R_c) is generally applied, irrespective of the plant species and NH₃ concentration. This study determined the effect of NH₃ concentration on deposition processes to individual moorland species. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to Deschampsia cespitosa (L.) Beauv., Calluna vulgaris (L.) Hull, Eriophorum vaginatum L., Cladonia spp., Sphagnum spp., and Pleurozium schreberi (Brid.) Mitt. Measurements were conducted across a wide range of NH₃ concentrations (1–140 μg m⁻³).NH₃ concentration directly affects the deposition processes to the vegetation canopy, with R_c, and cuticular resistance (R_w) increasing with increasing NH₃ concentration, for all the species and vegetation communities tested. For example, the R_c for C. vulgaris increased from 14 s m⁻¹ at 2 μg m⁻³ to 112 s m⁻¹ at 80 μg m⁻³. Diurnal variations in NH₃ uptake were observed for higher plants, due to stomatal uptake; however, no diurnal variations were shown for non-stomatal plants. R_c for C. vulgaris at 80 μg m⁻³ was 66 and 112 s m⁻¹ during day and night, respectively. Differences were found in NH₃ deposition between plant species and vegetation communities: Sphagnum had the lowest R_c (3 s m⁻¹ at 2 μg m⁻³ to 23 at 80 μg m⁻³), and D. cespitosa had the highest nighttime value (18 s m⁻¹ at 2 μg m⁻³ to 197 s m⁻¹ at 80 μg m⁻³).     

Gas-phase chemistry of benzyl alcohol: Reaction rate constants and products with OH radical and ozone

A bimolecular rate constant, k_{OH+Benzyl alcohol}, of (28 ± 7) × 10^?12 cm³ molecule^?1 s^?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with benzyl alcohol, at (297 ± 3) K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, k_{O3+Benzyl alcohol}, of approximately 6 × 10^?19 cm³ molecule^?1 s^?1 was determined by monitoring the decrease in benzyl alcohol concentration over time in an excess of ozone (O₃). To more clearly define part of benzyl alcohol's indoor environment degradation mechanism, the products of the benzyl alcohol + OH were also investigated. The derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to positively identify benzaldehyde, glyoxal and 4-oxopentanal as benzyl alcohol/OH reaction products. The elucidation of other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible benzyl alcohol/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms.     

Ozone response to precursor controls: comparison of data analysis methods with the predictions of photochemical air quality simulation models

Comparisons were made between the predictions of six photochemical air quality simulation models (PAQSMs) and three indicators of ozone response to emission reductions: the ratios of O₃/NO_z and O₃/NO_y and the extent of reaction. The values of the two indicator ratios and the extent of reaction were computed from the model-predicted mixing ratios of ozone and oxidized nitrogen species and were compared to the changes in peak 1 and 8 h ozone mixing ratios predicted by the PAQSMs. The ozone changes were determined from the ozone levels predicted for base-case emission levels and for reduced emissions of volatile organic compounds (VOCs) and oxides of nitrogen (NO_x). For all simulations, the model-predicted responses of peak 1 and 8 h ozone mixing ratios to VOC or NO_x emission reductions were correlated with the base-case extent of reaction and ratios of O₃/NO_z and O₃/NO_y. Peak ozone values increased following NO_x control in 95% (median over all simulations) of the high-ozone (>80 ppbv hourly mixing ratio in the base-case) grid cells having mean afternoon O₃/NO_z ratios less than 5 : 1, O₃/NO_y less than 4 : 1, or extent less than 0.6. Peak ozone levels decreased in response to NO_x reductions in 95% (median over all simulations) of the grid cells having peak hourly ozone mixing ratios greater than 80 ppbv and where mean afternoon O₃/NO_z exceeded 10 : 1, O₃/NO_y was greater than 8 : 1, or extent exceeded 0.8. Ozone responses varied in grid cells where O₃/NO_z was between 5 : 1 and 10 : 1, O₃/NO_y was between 4 : 1 and 8 : 1, or extent was between 0.6 and 0.8. The responses in such grid cells were affected by ozone responses in upwind grid cells and by the changes in ozone levels along the upwind boundaries of the modeling domains.     

Concentration-dependent NH3 deposition processes for mixed moorland semi-natural vegetation

Dry deposition modelling typically assumes that canopy resistance (R_c) is independent of ammonia (NH₃) concentration. An innovative flux chamber system was used to provide accurate continuous measurements of NH₃ deposition to a moorland composed of a mixture of Calluna vulgaris (L.) Hull, Eriophorum vaginatum L. and Sphagnum spp. Ammonia was applied at a wide range of concentrations (1–100 μg m⁻³). The physical and environmental properties and the testing of the chamber are described, as well as results for the moorland vegetation using the ‘canopy resistance’ and ‘canopy compensation point’ interpretations of the data.Results for moorland plant species demonstrate that NH₃ concentration directly affects the rate of NH₃ deposition to the vegetation canopy, with R_c and cuticular resistance (R_w) increasing with increasing NH₃ concentrations. Differences in R_c were found between night and day: during the night R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 95 s m⁻¹ at 80 μg m⁻³, whereas during the day R_c increases from 17 s m⁻¹ at 10 μg m⁻³ to 48 s m⁻¹ at 80 μg m⁻³. The lower resistance during the day is caused by the stomata being open and available as a deposition route to the plant. R_w increased with increasing NH₃ concentrations and was not significantly different between day and night (at 80 μg m⁻³ NH₃ day R_w=88 s m⁻¹ and night R_w=95 s m⁻¹). The results demonstrate that assessments using fixed R_c will over-estimate NH₃ deposition at high concentrations (over ∼15 μg m⁻³).     

The effect of diet manipulation on nitrous oxide and methane emissions from manure application to incubated grassland soils

Changes to agricultural management, particularly of the nitrogen (N) input to farms, have great potential for mitigating emissions of N containing gases, especially the greenhouse gas nitrous oxide (N₂O). Manipulating diets fed to livestock is a potential method for controlling N excretion and emissions of greenhouse gases (GHG's) to the atmosphere. We selected three slurries derived from sheep that had been fed, either ensiled ryegrass (Lolium hybridicum), lucerne (Medicago sativa) or kale (Brassica oleracea) and applied them to a grassland soil from the UK in a laboratory experiment using a special He/O₂ atmosphere incubation facility. The resulting fluxes of N₂O, CH₄ and N₂ were measured, with the largest total N fluxes generated by the ryegrass slurry treatment (14.23 ryegrass, 10.84 lucerne, 13.88 kale and 4.40 kg N ha⁻¹ from the control). Methane was emitted only from the ryegrass slurry treatment. The isotopomer signatures for N₂O in the control and lucerne slurry treatments indicated that denitrification was the main process responsible for N₂O emissions.     

Air quality measurements in urban green areas – a case study

The influence of traffic-induced pollutants (e.g. CO, NO, NO₂ and O₃) on the air quality of urban areas was investigated in the city of Essen, North Rhine-Westphalia (NRW), Germany. Twelve air hygiene profile measuring trips were made to analyse the trace gas distribution in the urban area with high spatial resolution and to compare the air hygiene situation of urban green areas with the overall situation of urban pollution. Seventeen measurements were made to determine the diurnal concentration courses within urban parks (summer conditions: 13 measurements, 530 30 min mean values, winter conditions: 4 measurements, 128 30 min mean values). The measurements were carried out during mainly calm wind and cloudless conditions between February 1995 and March 1996. It was possible to establish highly differentiated spatial concentration patterns within the urban area. These patterns were correlated with five general types of land use (motorway, main road, secondary road, residential area, green area) which were influenced to varying degrees by traffic emissions. Urban parks downwind from the main emission sources show the following typical temporal concentration courses: In summer rush-hour-dependent CO, NO and NO₂ maxima only occurred in the morning. A high NO₂/NO ratio was established during weather conditions with high global radiation intensities (K>800 W m⁻²), which may result in a high O₃ formation potential. Some of the values measured found in one of the parks investigated (Gruga Park, Essen, area: 0.7 km²), which were as high as 275 μg m⁻³ O₃ (30-min mean value) were significantly higher than the German air quality standard of 120 μg m⁻³ (30-min mean value, VDI Guideline 2310, 1996) which currently applies in Germany and about 20% above the maximum values measured on the same day by the network of the North Rhine–Westphalian State Environment Agency. In winter high CO and NO concentrations occur in the morning and during the afternoon rush-hour. The highest concentrations (CO=4.3 mg m⁻³, NO=368 μg m⁻³, 30-min mean values) coincide with the increase in the evening inversion. The maximum measured values for CO, NO and NO₂ do not, however, exceed the German air quality standards in winter and summer.     

Impact of permanent inundation on methane emissions from a Spartina alterniflora coastal salt marsh

To understand the effect of water level on CH₄ emissions from an invasive Spartina alterniflora coastal brackish marsh, we measured CH₄ emissions from intermittently and permanently (5 cm water depth) inundated mesocosms with or without N fertilizer added at a rate of 2.7 g N m^?2. Dissolved CH₄ concentrations in porewater and vertically-profiled sediment redox potential were measured, as were aboveground biomass and stem density of S. alterniflora. Mean CH₄ fluxes during the growing season in permanently inundated mesocosms without and with N fertilizer were 1.03 and 1.73 mg CH₄ m^?2 h^?1, respectively, which were significantly higher than in the intermittently inundated mesocosms. This response indicates that prolonged submergence of sediment, up to a water depth of 5 cm, stimulated CH₄ release. Inundation did not greatly affect aboveground biomass and stem density, but did significantly reduce redox potential in sediment, which in turn stimulated CH₄ production and increased the CH₄ concentration of porewater, resulting in higher CH₄ emission in the mesocosm. Our data showed that the stimulatory effect of shallow, permanent inundation on CH₄ emission in S. alterniflora marsh sediment was due primarily to an improved methanogenic environment rather than an increase in plant-derived substrates and/or the number of gas emission pathways through the plant’s aerenchymal system.     

Kinetics of the gas-phase reactions of NO3 radicals with ethyl acrylate,n-butyl acrylate,methyl methacrylate and ethyl methacrylate

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO₃ radicals with a series of acrylate esters: ethyl acrylate (k₁), n-butyl acrylate (k₂), methyl methacrylate (k₃) and ethyl methacrylate (k₄) at 298 ± 1 K and 760 Torr. The obtained rate constants are k₁ = (1.8 ± 0.25) × 10^?16 cm³ molecule^?1 s^?1, k₂ = (2.1 ± 0.33) × 10^?16 cm³ molecule^?1 s^?1, k₃ = (3.6 ± 1.2) × 10^?15 cm³ molecule^?1 s^?1, k₄ = (4.9 ± 1.7) × 10^?15 cm³ molecule^?1 s^?1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO₃ radicals. In addition, the atmospheric lifetimes of the compound against NO₃ attack are estimated and the results show that NO₃ reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.     

PM2.5 particles and size-segregated ionic species measured during fall season in three urban sites in Korea

Twelve hours integrated fine particles (PM_2.5) and 24-h average size-segregated particles were collected to investigate the chemical characteristics and to determine the size distribution of ionic species during October–December 1999 in three cities of different urban scale; Chongju, Kwangju, and Seoul, Korea. Concentrations of 5-min PM_2.5 black carbon (BC) and hourly criteria air pollutants (PM₁₀, CO, NO_x, SO₂, and O₃) were also measured using the Aethalometer and ambient air monitoring system, respectively.Highest PM_2.5 mass concentrations at Chongju, Kwangju, and Seoul sites were 63.0, 77.9, and 143.7 μg m⁻³, respectively. For the time period when highest PM_2.5 mass occurred, BC level out of PM_2.5 chemical species was highest at both Chongju and Kwangju, and highest NO₃⁻ (23.6 μg m⁻³) followed by BC (23.1 μg m⁻³) were observed at Seoul site, indicating that highest PM_2.5 pollution is closely associated with the traffic emissions. Strong relationships of Fe with BC and Zn at both Kwangju and Seoul sites support that the Fe and Zn measured there are originated partly from same source as BC, i.e. diesel traffics. However, it is suggested that the Fe measured at Chongju is most likely derived from dispersion of soil dust.The size distributions of SO₄²⁻, NO₃⁻, and NH₄⁺ ionic species indicated similar unimodal distributions at all sampling sites. However, different unimodal patterns in the accumulation mode size range with a peak in the smaller size (0.28–0.53 μm, condensation mode) in both Kwangju and Seoul, and in the relatively larger size (0.53–1.0 μm, droplet mode) in Chongju, were found. The potassium ion under the study sites dominates in the fine mode, and its size distribution showed unimodal character with a maximum in the size range 0.56–1.0 μm.     

Negative responses of Collembola in a forest soil (Alptal,Switzerland) under experimentally increased N deposition

The response of specific groups of organisms, like Collembola to atmospheric nitrogen (N) deposition is still scarcely known. We investigated the Collembola community in a subalpine forest (Alptal, Switzerland) as subjected for 12 years to an experimentally increased N deposition (+25 on top of ambient 12 kg N ha^?1 year^?1). In the 0–5 cm soil layer, there was a tendency of total Collembola densities to be lower in N-treated than in control plots. The density of Isotomiella minor, the most abundant species, was significantly reduced by the N addition. A tendency of lower Collembola group richness was observed in N-treated plots. The Density-Group index (d_DG) showed a significant reduction of community diversity, but the Shannon–Wiener index (H′) was not significantly affected by the N addition. The Collembola community can be considered as a bioindicator of N inputs exceeding the biological needs, namely, soil N saturation.     

Air quality in Brunei Darussalam during the 1998 haze episode

Regional haze from biomass burning in SE Asia is a recurring air pollution phenomenon with a potential impact on the health of several hundred million people. Air quality data in Brunei Darussalam during the 1998 haze episode revealed that only particulate matter is a significant pollutant. The WHO guideline of 70 μg m⁻³ for PM₁₀ (24 h average) was exceeded on 54 days during the haze episode which lasted from 1 February to 30 April 1998. Concentrations of SO₂, NO₂, and O₃ were all below WHO guidelines and the 8 h guideline for CO was exceeded on only seven occasions. Average daily PM₁₀ concentrations were below 450 μg m⁻³ but concentrations greater than 600 μg m⁻³ persisted for several hours at a time and total exposure to such high concentrations could add up to several days over the course of a haze episode. Airborne particles exhibited diurnal variation, typically rising through the night to very high levels in the early morning and thereafter decreasing due largely to meteorological factors. The pollutant standards index (PSI), widely used to report urban air quality, may not be suitable for haze from forest fires as it does not take into account short-term exposure to extremely high particle concentrations of up to 1 mg m⁻³.     

Measurement and analysis of atmospheric ammonia emissions from anaerobic lagoons

Ammonia-nitrogen flux (NH₃-N=(14/17)NH₃) was determined from six anaerobic swine waste storage and treatment lagoons (primary, secondary, and tertiary) using the dynamic chamber system. Measurements occurred during the fall of 1998 through the early spring of 1999, and each lagoon was examined for approximately one week. Analysis of flux variation was made with respect to lagoon surface water temperature (∼15 cm below the surface), lagoon water pH, total aqueous phase NH_x(=NH₃+NH₄⁺) concentration, and total Kjeldahl nitrogen (TKN). Average lagoon temperatures (across all six lagoons) ranged from approximately 10.3 to 23.3^°C. The pH ranged in value from 6.8 to 8.1. Aqueous NH_x concentration ranged from 37 to 909 mg N l⁻¹, and TKN varied from 87 to 950 mg N l⁻¹. Fluxes were the largest at the primary lagoon in Kenansville, NC (March 1999) with an average value of 120.3 μg N m⁻² min⁻¹, and smallest at the tertiary lagoon in Rocky Mount, NC (November 1998) at 40.7 μg N m⁻² min⁻¹. Emission rates were found to be correlated with both surface lagoon water temperature and aqueous NH_x concentration. The NH₃-N flux may be modeled as ln(NH₃-N flux)=1.0788+0.0406T_L+0.0015([NH_x]) (R²=0.74), where NH₃-N flux is the ammonia flux from the lagoon surface in μg N m⁻² min⁻¹, T_L is the lagoon surface water temperature in ^°C, and [NH_x] is the total ammonia-nitrogen concentration in mg N l⁻¹.     

Night-time tropospheric chemistry of the unsaturated alcohols (Z)-pent-2-en-1-ol and pent-1-en-3-ol: Kinetic studies of reactions of NO3 and N2O5 with stress-induced plant emissions

The night-time tropospheric chemistry of two stress-induced volatile organic compounds (VOCs), (Z)-pent-2-en-1-ol and pent-1-en-3-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO₃) with these pentenols were measured using the discharge-flow technique. Because of the relatively low volatility of these compounds, we employed off-axis continuous-wave cavity-enhanced absorption spectroscopy for detection of NO₃ in order to be able to work in pseudo first-order conditions with the pentenols in large excess over NO₃. The rate coefficients were determined to be (1.53±0.23)×10⁻¹³ and (1.39±0.19)×10⁻¹⁴ cm³ molecule⁻¹ s⁻¹ for reactions of NO₃ with (Z)-pent-2-en-1-ol and pent-1-en-3-ol. An attempt to study the kinetics of these reactions with a relative-rate technique, using N₂O₅ as source of NO₃ resulted in significantly higher apparent rate coefficients. Performing relative-rate experiments in known excesses of NO₂ allowed us to determine the rate coefficients for the N₂O₅ reactions to be (5.0±2.8)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ for (Z)-pent-2-en-1-ol, and (9.1±5.8)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ for pent-1-en-3-ol. We show that these relatively slow reactions can indeed interfere with rate determinations in conventional relative-rate experiments.     

Nitrous oxide emissions from mineral and organic soils of a Norway spruce stand in South–West Germany

Due to the high temporal and spatial variability of N₂O fluxes, estimates of N₂O emission from temperate forest ecosystems are still highly uncertain, particularly at larger scales. Although highest N₂O emissions with up to 7.0 kg N ha⁻¹ yr⁻¹ were mainly reported for soils affected by stagnant water, most of the reported gas flux measurements were performed at forest sites with well-aerated soils yielding mostly to low mean annual emission rates less than 1.0 kg N ha⁻¹ yr⁻¹. This study compares N₂O fluxes from upland (Cambisols) and temporally water-logged (Gleysols, Histosols) soils of the Central Black Forest (South-West Germany) over a period of 2 yr. Mean annual N₂O fluxes from investigated soils ranged between 0.2 and 3.9 kg N ha⁻¹ yr⁻¹. The fluxes showed a large variability between the different soil types. Emissions could be clearly ranked in the following order: Cambisols (0.26–0.75 kg N ha⁻¹ yr⁻¹)<Gleysols (1.37–2.68 kg N ha⁻¹ yr⁻¹)<Histosol (3.66–3.95 kg N ha⁻¹ yr⁻¹). Although the Cambisols cover two-thirds of the investigated area, only about half of the overall N₂O is emitted from this soil type. Therefore, regional or national N₂O fluxes from temperate forest soils are underestimated if soils characterised by intermediate aeration conditions are disregarded.     

Estimation of ecotoxicity of petroleum hydrocarbon mixtures in soil based on HPLC–GCXGC analysis

Detailed HPLC–GCXGC/FID (high performance liquid chromatography followed by comprehensive two-dimensional gas chromatography with flame-ionization detection) analysis of oil-contaminated soils was performed to interpret results of selected acute ecotoxicity assays. For the five ecotoxicity assays tested, plant seed germination and Microtox^® were selected as most sensitive for evaluating ecotoxicity of the oil in the soil phase and in the leaching water, respectively. The measured toxicity for cress when testing the soil samples did not correspond to TPH concentration in the soil. A detailed chemical composition analysis of the oil contamination using HPLC–GCXGC/FID allows to better predict the ecotoxicological risk and leaching potential of petroleum hydrocarbons in soil. Cress biomass production per plant was well correlated to the total aromatic hydrocarbon concentration (R² = 0.79, n = 6), while cress seed germination was correlated (R² = 0.82, n = 6) with total concentration of “highly water-soluble aromatic hydrocarbons” (HSaromatics). The observed ecotoxicity of the leaching water for Microtox-bacteria related well to calculated (based on the HPLC–GCXGC/FID results) petroleum hydrocarbon equilibrium concentrations in water.     

Laboratory studies on the uptake of aromatic hydrocarbons by ice crystals during vapor depositional crystal growth

Uptake of aromatic hydrocarbons (AH) by ice crystals during vapor deposit growth was investigated in a walk-in cold chamber at temperatures of 242, 251, and 260 K, respectively. Ice crystals were grown from ambient air in the presence of gaseous AH namely: benzene (C₆H₆), toluene (methylbenzene, C₇H₈), the C₈H₁₀ isomers ethylbenzene, o-, m-, p-xylene (dimethylbenzenes), the C₉H₁₂ isomers n-propylbenzene, 4-ethyltoluene, 1,3,5-trimethylbenzene (1,3,5-TMB), 1,2,4-trimethylbenzene (1,2,4-TMB), 1,2,3-trimethylbenzene (1,2,3-TMB), and the C₁₀H₁₄ compound tert.-butylbenzene. Gas-phase concentrations calculated at 295 K were 10.3–20.8 μg m⁻³. Uptake of AH was detected by analyzing vapor deposited ice with a very sensitive method composed of solid-phase micro-extraction (SPME), followed by gas chromatography/mass spectrometry (GC/MS).Ice crystal size was lower than 1 cm. At water vapor extents of 5.8, 6.0 and 8.1 g m⁻³, ice crystal shape changed with decreasing temperatures from a column at a temperature of 260 K, to a plate at 251 K, and to a dendrite at 242 K. Experimentally observed ice growth rates were between 3.3 and 13.3×10⁻³ g s⁻¹ m⁻² and decreased at lower temperatures and lower value of water vapor concentration. Predicted growth rates were mostly slightly higher.Benzene, toluene, ethylbenzene, and xylenes (BTEX) were not detected in ice above their detection limits (DLs) of 25 pg g_ice⁻¹ (toluene, ethylbenzene, xylenes) and 125 pg g_ice⁻¹ (benzene) over the entire temperature range. Median concentrations of n-propylbenzene, 4-ethyltoluene, 1,3,5-TMB, tert.-butylbenzene, 1,2,4-TMB, and 1,2,3-TMB were between 4 and 176 pg g_ice⁻¹ at gas concentrations of 10.3–10.7 μg m⁻³ calculated at 295 K. Uptake coefficients (K) defined as the product of concentration of AH in ice and density of ice related to the product of their concentration in the gas phase and ice mass varied between 0.40 and 10.23. K increased with decreasing temperatures. Values of Gibbs energy (ΔG) were between −4.5 and 2.4 kJ mol⁻¹ and decreased as temperatures were lowered. From the uptake experiments, the uptake enthalpy (ΔH) could be determined between −70.6 and −33.9 kJ mol⁻¹. The uptake entropy (ΔS) was between −281.3 and −126.8 J mol⁻¹ K⁻¹. Values of ΔH and ΔS were rather similar for 4-ethlytoluene, 1,3,5-TMB and tert.-butylbenzene, whereas 1,2,3-TMB showed much higher values.