Determination of PAN,PPN, PnBN and selected pentyl nitrates in Athens,Greece

Quasi-continuous measurements of PAN, PPN, PnBN and the alkyl nitrates—2-methyl-2-butyl nitrate, 3-pentyl nitrate and 2-pentyl nitrate were carried out in Athens using a simple cryoconcentration technique. The maximum mixing ratios measured were 6.6, 1.0 and 0.07 ppbv for PAN, PPN and PnBN, respectively, for the peroxyacyl nitrates, and 0.3, 0.09 and 0.03 ppb for 2-methyl-2-butyl nitrate, 2-pentyl nitrate and 3-pentyl nitrate, respectively. Mean ratios of PPN/PAN mixing ratios were 0.102 and of PnBN/PAN 0.012. 2PN/3PN mean ratios were 1.8 near the theoretical value of 1.6. All maximum values of measured nitrogenous compounds were associated with maximum mixing ratios of ozone and NO_x and occurred when southwestern winds prevailed in association with a temperature inversion.     

Seasonal characteristics of ambient volatile organic compounds in Seoul,Korea

The measurements of C₂–C₉ volatile organic compounds (VOC) were carried out at a site in Seoul, the capital of Korea from August 1998 to July 1999. Air samples were collected for 24 h in 6 l SUMMA canisters every 6 days. The canister samples were quantitatively analyzed by a GC/FID and GC/MS. The species with the highest mean concentration among the 70 identified was propane (7.8 ppb), followed by toluene (6.4 ppb) and ethylene (5.9 ppb). The high concentration of propane was mainly attributed to the emissions by liquefied petroleum gas (LPG) usage for cooking and heating, and butane fuel for transportation. The general trend of the seasonal variation shows higher concentrations in winter and lower ones in summer. This behavior was mainly caused by the variations of temperature, and resultant VOC source strengths, coupled with the variations of the mixing depth. According to the analysis of concentration ratios, the seasonal contributions of the major emission sources to the VOC concentrations were influenced by ambient temperature. Further, it was identified that the contributions by the use of solvents, natural gas, LPG, and butane fuel were closely related to the variations of consumption pattern according to seasons. Through the analysis of the concentration correlations between less reactive compound and highly reactive ones for summer and winter months, it was found that photochemical reactivity affects relative concentration of reactive compound.     

Ozone uptake by citrus trees exposed to a range of ozone concentrations

The Citrus genus includes a large number of species and varieties widely cultivated in the Central Valley of California and in many other countries having similar Mediterranean climates. In the summer, orchards in California experience high levels of tropospheric ozone, formed by reactions of volatile organic compounds (VOC) with oxides of nitrogen (NO_x). Citrus trees may improve air quality in the orchard environment by taking up ozone through stomatal and non-stomatal mechanisms, but they may ultimately be detrimental to regional air quality by emitting biogenic VOC (BVOC) that oxidize to form ozone and secondary organic aerosol downwind of the site of emission. BVOC also play a key role in removing ozone through gas-phase chemical reactions in the intercellular spaces of the leaves and in ambient air outside the plants. Ozone is known to oxidize leaf tissues after entering stomata, resulting in decreased carbon assimilation and crop yield. To characterize ozone deposition and BVOC emissions for lemon (Citrus limon), mandarin (Citrus reticulata), and orange (Citrus sinensis), we designed branch enclosures that allowed direct measurement of fluxes under different physiological conditions in a controlled greenhouse environment. Average ozone uptake was up to 11 nmol s^?1 m^?2 of leaf. At low concentrations of ozone (40 ppb), measured ozone deposition was higher than expected ozone deposition modeled on the basis of stomatal aperture and ozone concentration. Our results were in better agreement with modeled values when we included non-stomatal ozone loss by reaction with gas-phase BVOC emitted from the citrus plants. At high ozone concentrations (160 ppb), the measured ozone deposition was lower than modeled, and we speculate that this indicates ozone accumulation in the leaf mesophyll.     

Annual evolution and generation mechanisms of particulate nitrate in Madrid

During the course of one year (March 2004–March 2005), PM_2.5 particulate nitrate concentrations were semi-continuously measured every 10 min at a Madrid suburban site using the Rupprecht and Patashnick Series 8400N Ambient Particulate Nitrate Monitor (8400N). Gaseous pollutants (NO, NO₂, O₃, HCHO, HNO₂) were simultaneously measured with a DOAS spectrometer (OPSIS AR-500) and complementary meteorological information was obtained by a permanent tower. The particulate nitrate concentrations ranged from the instrumental detection limit of around 0.2 μg m⁻³, up to a maximum of about 25 μg m⁻³. The minimum monthly average was reached during August (0.32 μg m⁻³) and the maximum during November (3.0 μg m⁻³). Due to the semi-volatile nature of ammonium nitrate, peaks were hardly present during summer air pollution episodes. A typical pattern during days with low dispersive conditions was characterized by a steep rise of particulate nitrate in the morning, reaching maximum values between 9 and 14 UTC, followed by a decrease during the evening. On some occasions a light increase was observed at nighttime. During spring episodes, brief diurnal nitrate peaks were recorded, while during the autumn and winter episodes, later and broader nitrate peaks were registered. Analysis of particulate nitrate and related gaseous species indicated the photo-chemical origin of the morning maxima, delayed with respect to NO and closely associated with secondary NO₂ maximum values. The reverse evolution of nitrate and nitrous acid was observed after sunrise, suggesting a major contribution from HNO₂ photolysis to OH formation at this time of the day, which would rapidly produce nitrate in both gaseous and particulate phase. Some nocturnal nitrate maxima appeared under high humidity conditions, and a discussion about their origin involving different possible mechanisms is presented, i.e. the possibility that these nocturnal maximum values could be related to the heterogeneous formation of nitrous and nitric acid by the hydrolysis of NO₂ on wet aerosols.     

The impact of an 8 h ozone air quality standard on ROG and NOx controls in Southern California

The new National Ambient Air Quality Standard for ozone in the US uses 8 h averaging for the concentration. Based on the 1993 ambient data for Southern California, 8 h averaging has a moderate tendency to move the location of the peak ozone concentration east of the location of the peak 1 h ozone concentration. Reducing the area-wide peak 8 h ozone concentration to 80 ppb would require an effective reduction of the area-wide peak 1 h ozone concentration to around 90 ppb. The Urban Airshed Model with improved numerical solvers, meteorological input based on a mesoscale model and an adjusted emissions inventory was used to study the effect of reactive organic gases (ROG) and NO_x controls on daily-maximum and peak 8 h ozone concentrations under the 26–28 August 1987 ozone episodic conditions in Southern California. The NO_x disbenefit remains prominent for the case of 8 h ozone concentration but is somewhat less prominent, especially when areal ozone exposure is considered, than the case for 1 h ozone concentration. The role of two indicators – O₃/NO_y and H₂O₂/HNO₃ – for NO_x- and ROG-sensitivity for 1 and 8 h ozone concentrations were also studied. In general, the indicator trends are consistent with model predictions, but the discriminating power of the indicators is rather limited.     

Surface ozone and NOx concentrations at a high altitude Mediterranean site,Greece

Ozone was measured in six- and NO_x in five sampling periods in 1996–97, mostly during summer, at a 1070 m altitude site in northern Peloponnese. Mean values in each sampling period ranged from 43–48 ppb exceeding the European Union 24 h plant protection standard. The background ozone concentration of 43 ppb derived from the correlation of ozone with NO^′_x also exceeded the EU plant protection standard. Ozone exhibited maxima in the afternoon and minima during the night; in certain 24–48 h periods, however, the ozone concentrations remained practically constant; in these short periods air mass back trajectories indicated air masses which originated in north Africa. NO^′_x concentrations had maximum of 24 h around noon. Their mean concentrations ranged from 0.5–0.7 ppb, smaller than respective concentrations in north-central Europe.     

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.     

Long-term observation of nitrate radicals in the continental boundary layer near Berlin

Long-term observations of the nitrate radical concentration and supporting parameters in the continental boundary layer at the rural site Lindenberg near Berlin, Germany, were performed using differential optical absorption spectroscopy (DOAS). Average nighttime NO₃ levels were 4.6 ppt, while NO₃ steady-state lifetimes (calculated from the NO₂–O₃ product and the NO₃ concentration) varied between 5 s and 615 s with an average of 92 s. The long-term observations offered the possibility to study the importance of NO₃ for the oxidation of VOCs (volatile organic compounds) and its contribution in the non-photochemical removal of NO_x from the atmosphere in different seasons. Analysis of the data showed, that NO₃ was depleted by both, reactions with VOCs and indirectly by loss of N₂O₅ on aerosol surfaces. A clear seasonal variation of the sink distribution was found. The VOC sink dominated during summer while indirect loss was of major importance during the winter months. The results are compared with former long-term campaigns of NO₃ in the marine boundary layer.     

Trace gas variations at Cape Point,South Africa,during May 1997 following a regional biomass burning episode

During the continuous monitoring of atmospheric parameters at the station Cape Point (34°S, 18°E), a smoke plume originating from a controlled fire of 30-yr-old fynbos was observed on 6 May 1997. For this episode, which was associated with a nocturnal inversion and offshore airflow, atmospheric parameters (solar radiation and meteorological data) were considered and the levels of various trace gases compared with those measured at Cape Point in maritime air. Concentration maxima in the morning of 6 May for CO₂, CO, CH₄ and O₃ amounted to 370.3 ppm, 491 ppb, 1730 ppb and 47 ppb, respectively, whilst the mixing ratios of several halocarbons (F-11, F-12, F-113, CCl₄ and CH₃CCl₃) remained at background levels. In the case of CO, the maritime background level for this period was exceeded by a factor of 9.8. Differences in ozone levels of up to 5 ppb between air intakes at 4 and 30 m above the station (located at 230 m above sea level) indicated stratification of the air advected to Cape Point during the plume event. Aerosols within the smoke plume caused the signal of global solar radiation and UV–A to be attenuated from 52.4 to 13.0 mW cm⁻² and from 2.3 to 1.3 mW cm⁻², respectively, 5 h after the trace gases had reached their maxima. Emission ratios (ERs) calculated for CO and CH₄ relative to CO₂ mixing ratios amounted to 0.042 and 0.0040, respectively, representing one of the first results for fires involving fynbos. The CO ER is somewhat lower than those given in the literature for African savanna fires (average ER=0.048), whilst for CH₄ the ER falls within the range of ERs reported for the flaming (0.0030) and smouldering phases (0.0055) of savanna fires. Non-methane hydrocarbon (NMHC) data obtained from a grab sample collected during the plume event were compared to background levels. The highest ERs (ΔNMHC/ΔCH₄) have been obtained for the C₂–C₃ hydrocarbons (e.g. ethene at 229.3 ppt ppb⁻¹), whilst the C₄–C₇ hydrocarbons were characterised by the lowest ERs (e.g. n-hexane at 1.0 and n-pentane at 0.8 ppt ppb⁻¹).     

VOC concentration profiles in an ozone non-attainment area: A case study in an urban and industrial complex metroplex in southern Taiwan

VOCs are important precursors of the atmospheric ozone formation species. This study investigated the airborne concentrations of 52 VOCs at two air quality monitoring stations, Daliao and Tzouying, during wintertime in southern Taiwan. Airborne VOCs samples were taken in stainless steel canisters four times per day and analyzed via gas chromatography/mass spectrometry. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential in this ozone non-attainment region. Toluene, propane, isopentane, propene, n-butane, n-pentane and isoprene contributed 78–79% of the 52 VOCs in Daliao. Toluene, 1-butene, isopentane, propene, propane, n-undecane, and n-butane contributed 71–77% of the 52 VOCs in Tzouying. The VOCs concentrations were higher in Daliao due to the high toluene emissions from a paint plant and a solvent plant in the nearby industrial district. The 24-h VOC concentrations averaged 25 ppb higher in Tzouying than in Daliao. The ozone formation potential of airborne VOCs was 1687–2730 and 1717–2261 μg-O₃/g-VOCs in Daliao and Tzouying, respectively. Ozone concentrations in Tzouying were 44 ppb higher than in Daliao during the 1200–1600 sampling period.     

An empirical approach for the prediction of annual mean nitrogen dioxide concentrations in London

Annual mean limits for NO₂ concentrations have been set in the European Union, which will be most challenging to meet in large urban conurbations. In this paper, we discuss techniques that have been developed to predict current and future NO₂ concentrations in London, utilising ambient data. Hourly average NO_x (NO+NO₂) and NO₂ concentrations are used to calculate NO_x frequency distributions. By defining relationships between the annual mean NO_x and NO₂ at different sites, it is possible to investigate different NO_x reduction strategies. The application of the frequency distribution approach to monitoring sites in London shows that given the likely change in emissions by 2005, it is unlikely that much of central and inner London will meet the objective. The approaches used suggest that meeting the objective in central London will be the most challenging for policy makers requiring NO_x concentrations as low as 30 ppb, compared with values closer to 36–40 ppb for outer London. Predictions for 2005 indicate that concentrations of NO₂ up to 6 ppb in excess of the objective are likely in central London.     

Biogenic VOC emissions from fresh leaf mulch and wood chips of Grevillea robusta (Australian Silky Oak)

The emissions of VOC from freshly cut and shredded Grevillea robusta (Australian Silky Oak) leaves and wood have been measured. The VOC emissions from fresh leaf mulch and wood chips lasted typically for 30 and 20 h respectively, and consisted primarily of ethanol, (E)-2-hexenal, (Z)-3-hexen-1-ol and acetaldehyde. The integrated emissions of the VOCs were 0.38±0.04 g kg⁻¹ from leaf mulch, and 0.022±0.003 g kg⁻¹ from wood chips. These emissions represent a source of VOCs in urban and rural air that has previously been unquantified and is currently unaccounted for. These VOCs from leaf mulch and wood chips will contribute to both urban photochemistry and secondary organic aerosol formation. Any CH₄ emissions from leaf mulch and wood chips were <1×10⁻¹¹ g g dry mass⁻¹ s⁻¹.     

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.     

Estimation and characterization of children’s ambient generated exposure to PM2.5 using sulphate and elemental carbon as tracers

Children’s exposures to ambient and non-ambient fine particulate matter (PM_2.5) were determined using the sulphate and elemental carbon components of the PM_2.5 mixture as tracers of the ambient contribution during a 6-week winter period in Prince George, British Columbia, Canada. Personal exposures to PM_2.5 were measured in children at 5 elementary schools located throughout the city and ambient samples were collected on school rooftops. Average ambient levels and personal exposures during this time period were 13.8 μg m^?3 and 16.4 μg m^?3 respectively. From the data pooled across individuals, use of the two different tracers indicated identical estimates of median exposure to ambient PM_2.5 (7.5 μg m^?3) and similar estimates of non-ambient generated exposure (6.4 and 5.0 μg m^?3) and infiltration (0.49 and 0.52) for the sulphate and elemental carbon approach, respectively. The median fraction of the ambient concentration resulting in exposure or exposure factors were 0.54 and 0.55 respectively, however lower values of 0.46 and 0.42 were determined from regression analysis. A strong association was found between exposure to ambient PM_2.5 and measured ambient concentrations at both the closest school monitor (median r = 0.92) and a central site (median r = 0.88) demonstrating that the central site monitor was suitable for assessing longitudinal ambient generated exposure throughout the city. These results support the use of elemental carbon as a tracer of ambient generated exposure and the use of ambient data as estimates of longitudinal changes in children’s exposure in this setting. The importance of both ambient and non-ambient sources of PM_2.5 is emphasized by their almost equal contribution to total personal exposures. Comparison with other studies suggests a limited influence of climate and the cold season in Prince George on exposure levels and found similar mean non-ambient generated exposures despite large variability across and within subjects in any given location.     

Use of passive samplers to measure atmospheric ammonia levels in a high-density industrial hog farm area of eastern North Carolina

Hog concentrated animal feeding operations (CAFOs) in North Carolina release ammonia (NH₃), hydrogen sulfide, VOCs, and particulate matter to the atmosphere. These operations are located mainly in the NC coastal plain and can create potential health hazards for nearby human populations. Limited work has been performed to measure NH₃ at the community level to assess potential human exposure. In an effort to address this issue, a study was designed to measure NH₃ levels near hog CAFOs and community locations (i.e. homes and schools) in Eastern NC.NH₃ was collected using passive diffusion tubes in triplicate exposed primarily in weekly intervals. Sampling occurred from October 2003 to May 2004 (20 sites) and from July 2004 to October 2004 (23 sites) at varying distances from hog CAFOs in close proximity to homes and schools. Average weekly NH3 levels were measured as mass (μg NH₃-N) and converted to concentration (ppb). Mean level of 13.8 ppb near homes and schools (<2 km) was 4–12 times greater than ambient background levels (1–3 ppb), reaching as high as 80 ppb. Exposed sites (<2 km from a hog CAFO) had a mean level of 12.8 ppb which was over 2 times higher than the mean level of 5.5 ppb at less exposed sites (>2 km from a hog CAFO).The study establishes that passive sampling can be effectively used to measure average atmospheric ammonia levels at community locations near hog CAFOs in Eastern NC. The collected data indicate the relative exposure for human populations who live near a hog CAFO. The closer a populace is to the hog CAFO, the more intense the exposure. These results require more validation in the field by comparison to a reference method.     

HNO3 analyzer by scrubber difference and the NO–ozone chemiluminescence method

A fast response analyzer for HNO₃ in highly polluted air is described. The time resolution attainable was 12 s. The method is based on the difference in a technique for HNO₃-scrubbed and non-scrubbed air and the reduction of HNO₃ to NO with the use of a line of catalytic converters and a method for the subsequent NO-ozone chemiluminescence. A sample air stream, in which particulates are removed with a Teflon filter, is divided into two channels. CH-1 is directly connected to the converter line, and CH-2 contains a HNO₃ scrubber packed with a nylon fiber that goes to another converter line. Each converter line is composed of a hot quartz-bead converter (QBC) and a molybdenum converter (MC) in a series. A QBC reduces HNO₃ to (NO+NO₂), which is called NO_x. The MC reduces the NO_x to NO.For CH-1, the analyzer detects most compounds that typically comprise NO_y (J. Geophys. Res. 91 (1986) 9781). These CH-1 compounds are called NO_y′ hereafter (NO_y-particulate nitrate) because the particulates are removed by the filter. A difference in the detector signal for the two channels indicates HNO₃. For a blank test, atmospheric air in which HNO₃ was pre-scrubbed by an extra nylon fiber was introduced to the analyzer. Variations in the blank value were 0.38±0.42 and 0.34±0.55 ppb during the high readings (NO_y′-HNO₃ ) (called NO_y^* hereafter) (111±12 ppb, N=180), and low NO_y^* readings (62±8 ppb, N=180), respectively, indicating that the lowest detection limit of the analyzer is 1.1 ppb (2σ). When the data obtained with the analyzer is compared to the data using the denuder method, a linear correlation with the regression of Y=0.973X+0.077 (r²=0.916 (N=20)) in the range of 0–6.5 ppb HNO₃ is obtained, which is an excellent agreement. Atmospheric monitoring was carried out at Kobe. Although the average concentration of HNO₃ was 2.6±1.3 ppb, ca.10 ppb for a HNO₃ concentration was occasionally observed when the NO_y^* concentration was high, i.e., more than 100 ppb.     

Measurement and analysis of atmospheric concentrations of isoprene and its reaction products in central Texas

A field experiment was conducted in August 1998 to investigate the concentrations of isoprene and isoprene reaction products in the surface and mixed layers of the atmosphere in Central Texas. Measured near ground-level concentrations of isoprene ranged from 0.3 (lower limit of detection – LLD) to 10.2 ppbv in rural regions and from 0.3 to 6.0 ppbv in the Austin urban area. Rural ambient formaldehyde levels ranged from 0.4 ppbv (LLD) to 20.0 ppbv for 160 rural samples collected, while the observed range was smaller at Austin (0.4–3.4 ppbv) for a smaller set of samples (37 urban samples collected). Methacrolein levels did not vary as widely, with rural measurements from 0.1 ppbv (LLD) to 3.7 ppbv and urban concentrations varying between 0.2 and 5.7 ppbv. Isoprene flux measurements, calculated using a simple box model and measured mixed-layer isoprene concentrations, were in reasonable agreement with emission estimates based on local ground cover data. Ozone formation attributable to biogenic hydrocarbon oxidation was also calculated. The calculations indicated that if the ozone formation occurred at low VOC/NO_x ratios, up to 20 ppbv of ozone formed could be attributable to biogenic photooxidation. In contrast, if the biogenic hydrocarbon reaction products were formed under low NO_x conditions, ozone production attributable to biogenics oxidation would be as low as 1 ppbv. This variability in ozone formation potentials implies that biogenic emissions in rural areas will not lead to peak ozone levels in the absence of transport of NO_x from urban centers or large rural NO_x sources.     

Ambient sulfur dioxide,nitrogen dioxide,and ammonia at ten background and rural sites in China during 2007–2008

We present two years (January 2007–December 2008) of atmospheric SO₂, NO₂ and NH₃ measurements from ten background or rural sites in nine provinces in China. The measurements were made on a monthly basis using passive samplers under careful quality control. The results show large geographical and seasonal variations in the concentrations of these gases. The mean SO₂ concentration varied from 0.7 ± 0.4 ppb at Waliguan on Qinghai Plateau to 67.3 ± 31.1 ppb at Kaili in Guizhou province. The mean NO₂ concentration ranged from 0.6 ± 0.4 ppb at Waliguan to 23.9 ± 6.9 ppb at Houma in southern Shanxi. The mean NH₃ concentration ranged from 2.8 ± 3.0 ppb at Shangdianzi in northeastern Beijing to 13.7 ± 8.4 ppb at Houma. At most sites, SO₂ and NO₂ peaked in winter and reached minima in summer, while NH₃ showed maximum values in summer and lower values in cold seasons. On the whole, the geographical distributions of the observed gas concentrations are consistent with those of emissions. The ground measurements of SO₂ and NO₂ are contrasted to the SCIAMACHY SO₂ and OMI NO₂ tropospheric columns, respectively. Although the satellite data can capture the main features of emissions and concentrations of SO₂, they do not reflect the variations of SO₂ in the surface layer. The situation is better for the case of NO₂. The OMI NO₂ columns capture the geographical differences in the ground NO₂ and correlate fairly well with the ground levels of NO₂ at six of the ten sites.     

Seasonal soil VOC exchange rates in a Mediterranean holm oak forest and their responses to drought conditions

Available information on soil volatile organic compound (VOC) exchange, emissions and uptake, is very scarce. We here describe the amounts and seasonality of soil VOC exchange during a year in a natural Mediterranean holm oak forest growing in Southern Catalonia. We investigated changes in soil VOC dynamics in drought conditions by decreasing the soil moisture to 30% of ambient conditions by artificially excluding rainfall and water runoff, and predicted the response of VOC exchange to the drought forecasted in the Mediterranean region for the next decades by GCM and ecophysiological models.The annual average of the total (detected) soil VOC and total monoterpene exchange rates were 3.2±3.2 and −0.4±0.3 μg m⁻² h⁻¹, respectively, in control plots. These values represent 0.003% of the total C emitted by soil at the study site as CO₂ whereas the annual mean of soil monoterpene exchange represents 0.0004% of total C. Total soil VOC exchange rates in control plots showed seasonal variations following changes in soil moisture and phenology. Maximum values were found in spring (17±8 μg m⁻² h⁻¹). Although there was no significant global effect of drought treatment on the total soil VOC exchange rates, annual average of total VOC exchange rates in drought plots resulted in an uptake rate (−0.5±1.8 μg m⁻² h⁻¹) instead of positive net emission rates. Larger soil VOC and monoterpene exchanges were measured in drought plots than in control plots in summer, which might be mostly attributable to autotrophic (roots) metabolism.The results show that the diversity and magnitude of monoterpene and VOC soil emissions are low compared with plant emissions, that they are driven by soil moisture, that they represent a very small part of the soil-released carbon and that they may be strongly reduced or even reversed into net uptakes by the predicted decreases of soil water availability in the next decades. In all cases, it seems that VOC fluxes in soil might have greater impact on soil ecology than on atmospheric chemistry.     

Dry deposition of ammonia,nitric acid,ammonium, and nitrate to alpine tundra at Niwot Ridge,Colorado

Micrometeorological measurements and ambient air samples, analyzed for concentrations of NH₃, HNO₃, NH₄⁺, and NO₃⁻, were collected at an alpine tundra site on Niwot Ridge, Colorado. The measured concentrations were extremely low and ranged between 5 and 70 ng N m⁻³. Dry deposition fluxes of these atmospheric species were calculated using the micrometeorological gradient method. The calculated mean flux for NH₃ indicates a net deposition to the surface and indicates that NH₃ contributed significantly to the total N deposition to the tundra during the August–September measurement period. Our pre-measurement estimate of the compensation point for NH₃ in air above the tundra was 100–200 ng N m⁻³; thus, a net emission of NH₃ was expected given the low ambient concentrations of NH₃ observed. Based on our results, however, the NH₃ compensation point at this alpine tundra site appears to have been at or below about 20 ng N m⁻³. Large deposition velocities (>2 cm s⁻¹) were determined for nitrate and ammonium and may result from reactions with surface-derived aerosols.