Gap Filling and Quality Assessment of CO2 and Water Vapour Fluxes above an Urban Area with Radial Basis Function Neural Networks

Vertical turbulent fluxes of water vapour, carbon dioxide, and sensible heat were measured from 16 August to the 28 September 2006 near the city centre of Münster in north-west Germany. In comparison to results of measurements above homogeneous ecosystem sites, the CO₂ fluxes above the urban investigation area showed more peaks and higher variances during the course of a day, probably caused by traffic and other varying, anthropogenic sources. The main goal of this study is the introduction and establishment of a new gap filling procedure using radial basis function (RBF) neural networks, which is also applicable under complex environmental conditions. We applied adapted RBF neural networks within a combined modular expert system of neural networks as an innovative approach to fill data gaps in micrometeorological flux time series. We found that RBF networks are superior to multi-layer perceptron (MLP) neural networks in the reproduction of the highly variable turbulent fluxes. In addition, we enhanced the methodology in the field of quality assessment for eddy covariance data. An RBF neural network mapping system was used to identify conditions of a turbulence regime that allows reliable quantification of turbulent fluxes through finding an acceptable minimum of the friction velocity. For the data analysed in this study, the minimum acceptable friction velocity was found to be 0.15 m s⁻¹. The obtained CO₂ fluxes, measured on a tower at 65 m a.g.l., reached average values of 12 μmol m⁻² s⁻¹ and fell to nighttime minimum values of 3 μmol m ⁻² s⁻¹. Mean daily CO₂ emissions of 21 g CO₂ m⁻²d ⁻¹ were obtained during our 6-week experiment. Hence, the city centre of Münster appeared to be a significant source of CO₂. The half-hourly average values of water vapour fluxes ranged between 0.062 and 0.989 mmol m⁻² s⁻¹and showed lower variances than the simultaneously measured fluxes of CO₂.     

Carbon dioxide seasonality in dynamically ventilated caves: the role of advective fluxes

The seasonality in cave CO₂ levels was studied based on (1) a new data set from the dynamically ventilated Comblain-au-Pont Cave (Dinant Karst Basin, Belgium), (2) archive data from Moravian Karst caves, and (3) published data from caves worldwide. A simplified dynamic model was proposed for testing the effect of all conceivable CO₂ fluxes on cave CO₂ levels. Considering generally accepted fluxes, i.e., the direct diffusive flux from soils/epikarst, the indirect flux derived from dripwater degassing, and the input/output fluxes linked to cave ventilation, gives the cave CO₂ level maxima of 1.9 × 10⁻² mol m⁻³ (i.e., ∼ 440 ppmv), which only slightly exceed external values. This indicates that an additional input CO₂ flux is necessary for reaching usual cave CO₂ level maxima. The modeling indicates that the additional flux could be a convective advective CO₂ flux from soil/epikarst driven by airflow (cave ventilation) and enhanced soil/epikarstic CO₂ concentrations. Such flux reaching up to 170 mol s⁻¹ is capable of providing the cave CO₂ level maxima up to 3 × 10⁻² mol m⁻³ (70,000 ppmv). This value corresponds to the maxima known from caves worldwide. Based on cave geometry, three types of dynamic caves were distinguished: (1) the caves with the advective CO₂ flux from soil/epikarst at downward airflow ventilation mode, (2) the caves with the advective soil/epikarstic flux at upward airflow ventilation mode, and (3) the caves without any soil/epikarstic advective flux. In addition to CO₂ seasonality, the model explains both the short-term and seasonal variations in δ¹³C in cave air CO₂.

     

Net CO2 exchange of a subarctic mountain birch ecosystem

Summary  Net ecosystem CO₂ exchange was measured over a mountain birch forest in northern Finland throughout the growing season. The maximal net CO₂ uptake rate of about − 0.5 mg(CO₂) m⁻² s⁻¹ was observed at the end of July. The highest nocturnal respiration rates in early August were 0.2 mg(CO₂) m⁻² s⁻¹. The daily CO₂ balances during the time of maximal photosynthesis were about −15 g(CO₂) m⁻² d⁻¹. The mountain birch forest acted as a net sink of CO₂ from 30 June to 28 August. During that period the net CO₂ balance was −448 g(CO₂)m⁻². The interannual representativeness of the observed balances was studied using a simplified daily balance model, with daily mean global radiation and air temperature as the input parameters. The year-to-year variation in the phenological development was parameterised as a function of the cumulative effective temperature sum. The daily balance model was used for estimating the variability in the seasonal CO₂ balances due to the timing of spring and meteorological factors. The sink term of CO₂ in 1996 was lower than the 15-year mean, mainly due to the relatively late emergence of the leaves. Received October 11, 1999 Revised April 25, 2000     

Seasonal carbon dioxide balance and respiration of a high-arctic fen ecosystem in NE-Greenland

Summary  Turbulent fluxes of CO₂ were continuously measured by eddy correlation for three months in 1997 over a gramineous fen in a high-arctic environment at Zackenberg (74°28′12″N, 20°34′23″W) in NE-Greenland. The measurements started on 1 June, when there was still a 1–2 m cover of dry snow, and ended 26 August at a time that corresponds to late autumn at this high-arctic site. During the 20-day period with snow cover, fluxes of CO₂ to the atmosphere were small, typically 0.005 mg CO₂ m⁻² s⁻¹ (0.41 g CO₂ m⁻² d⁻¹), wheres during the thawed period, the fluxes displayed a clear diurnal variation. During the snow-free period, before the onset of vegetation growth, fluxes of CO₂ to the atmosphere were typically 0.1 mg CO₂ m⁻² s⁻¹ in the afternoon, and daily sums reached values up to almost 9 g CO₂ m⁻² d⁻¹. After 4 July, downward fluxes of CO₂ increased, and on sunny days in the middle of the growing season, the net ecosystem exchange rates attained typical values of about −0.23 mg m⁻² s⁻¹ at midday and max values of daily sums of −12 g CO₂ m⁻² d⁻¹. Throughout the measured period the fen ecosystem acted as a net-sink of 130 g CO₂ m⁻². Modelling the ecosystem respiration during the season corresponded well with eddy correlation and chamber measurements. On the basis of the eddy correlation data and the predicted respiration effluxes, an estimate of the annual CO₂ balance the calender year 1997 was calculated to be a net-sink of 20 g CO₂ m⁻² yr⁻¹. Received October 6, 1999 Revised May 2, 2000     

Effects of Irrigation on Nitrous Oxide, Methane and Carbon Dioxide Fluxes in an Inner Mongolian Steppe

Increased precipitation during the vegetation periods was observed in and further predicted for Inner Mongolia. The changes in the associated soil moisture may affect the biosphere-atmosphere exchange of greenhouse gases. Therefore, we set up an irrigation experiment with one watered （W） and one unwatered plot （UW） at a winter-grazed Leymus chinensis-steppe site in the Xilin River catchment, Inner Mongolia. UW only received the natural precipitation of 2005 （129 mm）, whereas W was additionally watered after the precipitation data of 1998 （in total 427 mm）. In the 3-hour resolution, we determined nitrous oxide （N20）, methane （CH4） and carbon dioxide （CO2） fluxes at both plots between May and September 2005, using a fully automated, chamber-based measuring system. N20 fluxes in the steppe were very low, with mean emissions （±s.e.） of 0.9-4-0.5 and 0.7-4-0.5 μg N m^-2 h^-1 at W and UW, respectively. The steppe soil always served as a CH4 sink, with mean fluxes of -24.1-4-3.9 and -31.1-4- 5.3 μg C m^-2 h^-1 at W and UW. Nighttime mean CO2 emissions were 82.6±8.7 and 26.3±1.7 mg C m^-2 h^-1 at W and UW, respectively, coinciding with an almost doubled aboveground plant biomass at W. Our results indicate that the ecosystem CO2 respiration responded sensitively to increased water input during the vegetation period, whereas the effects on CH4 and N2O fluxes were weak, most likely due to the high evapotranspiration and the lack of substrate for N2O producing processes. Based on our results, we hypothesize that with the gradual increase of summertime precipitation in Inner Mongolia, ecosystem CO2 respiration will be enhanced and CH4 uptake by the steppe soils will be lightly inhibited.     

Rain-aerosol coupling in the tropical atmosphere of Southeast Asia: distribution and scavenging ratios of major ionic species

Both aerosol and rainwater samples were collected and analyzed for ionic species at a coastal site in Southeast Asia over a period of 9 months (January–September 2006) covering different monsoons. In general, the occurrence and distribution of ionic species showed a distinct seasonal variation in response to changes in air mass origins. Real-time physical characterization of aerosol particles during rain events showed changes in particle number distributions which were used to assess particle removal processes associated with precipitation, or scavenging. The mean scavenging coefficients for particles in the range 10–500 nm and 500–10 μm were 7.0 × 10⁻⁵ ± 2.8 × 10⁻⁵ s⁻¹ and 1.9 × 10⁻⁴ ± 1.6 × 10⁻⁵ s⁻¹, respectively. A critical analysis of the scavenging coefficients obtained from this study suggested that the wet removal of aerosol particles was greatly influenced by rain intensity, and was particle size-dependent as well. The scavenging ratios, another parameter used to characterize particle removal processes by precipitation, for NH₄ ⁺, Cl⁻, SO₄ ²⁻, and NO₃ ⁻ were found to be higher than those of Na⁺, K⁺, and Ca²⁺ of oceanic and crustal origins. This enrichment implied that gaseous species NH₃, HCl, and HNO₃ could also be washed out readily. These additional sources of ions in precipitation presumably counter-balanced the dilution effect caused by high total precipitation volume in the marine and tropical area.     

General Characteristics of the Atmospheric Boundary Layer Over a Flaw Lead Polynya Region in Winter and Spring

A time series of microwave radiometric profiles over Arctic Canada’s Cape Bathurst (70°N, 124.5°W) flaw lead polynya region from 1 January to 30 June, 2008 was examined to determine the general characteristics of the atmospheric boundary layer in winter and spring. A surface based or elevated inversion was present on 97% of winter (January–March) days, and on 77% of spring (April–June) days. The inversion was the deepest in the first week of March (≈1100 m), and the shallowest in June (≈250 m). The mean temperature and absolute humidity from the surface to the top of the inversion averaged 250.1 K (−23.1°C), and 0.56 × 10⁻³ kg m⁻³ in winter, and in spring averaged 267.5 K (−5.6°C), and 2.77 × 10⁻³ kg m⁻³. The median winter atmospheric boundary-layer (ABL) potential temperature profile provided evidence of a shallow, weakly stable internal boundary layer (surface to 350 m) topped by an inversion (350–1,000 m). The median spring profile showed a shallow, near-neutral internal boundary layer (surface to 350 m) under an elevated inversion (600–800 m). The median ABL absolute humidity profiles were weakly positive in winter and negative in spring. Estimates of the convergence of sensible heat and water vapour from the surface that could have produced the turbulent internal boundary layers of the median profiles were 0.67 MJ m⁻² and 13.1 × 10⁻³ kg m⁻² for the winter season, and 0.66 MJ m⁻² and 33.4 × 10⁻³ kg m⁻² for the spring season. With fetches of 10–100 km, these accumulations may have resulted from a surface sensible heat flux of 15–185 W m⁻², plus a surface moisture flux of 0.001–0.013 mm h⁻¹ (or a latent heat flux of 0.7–8.8 W m⁻²) in winter, and 0.003–0.033 mm h⁻¹ (or a latent heat flux of 2–22 W m⁻²) in spring.     

Effect of diurnal and seasonal temperature variation on Cussac cave ventilation using co2 assessment

Cussac cave was investigated to assess the cave air temperature variations and to understand its ventilation regime. This cave is located in an active karst system in the south west part of France. It has a single entrance and is considered as a cold air trap. In this study, air mass exchanges were probed. Measurements of temperature and Pco₂ with a 30-min frequency were made in several locations close to the cave entrance. Speed of the air flow was also measured at the door of cave entrance. Results show that cave air Pco₂ varies from 0.18 to 3.33 %. This cave appears to be a CO₂ source with a net mass of 2319 tons blown in 2009. Carbon-stable isotope of CO₂ (¹³Cco₂) ranges from −20.6 ‰ in cold season to −23.8 ‰ in warm season. Cave air is interpreted as a result of a mix between external air and an isotopically depleted air, coming from the rock environment. The isotopic value of the light member varies through time, from −23.9 to −22.5 ‰. Furthermore, this study ascertains that the cave never stops in communicating with the external air. The ventilation regime is identified. (1) In cold season, the cave inhales at night and blows a little at the warmest hours. However, in warm season, (2) cave blows at night, but (3) during the day, a convection loop takes place in the entrance area and prevents the external air from entering the cave, confirming the cold air trap.

     

Hoarfrost and rime chemistry in Poland—An introductory analysis from meteorological perspective

Hoarfrost and rime analysis was based on the collection of samples between 2003 and 2006 from 8 sites, which represent both lowland (northern) and mountainous (southern) parts of Poland. On the other hand 4 of these sites belong to “urban” and 4 to “rural” category. pH, conductivity, SO₄²⁻, NO₃⁻, Cl⁻, H⁺, NH₄⁺, Ca²⁺, Mg²⁺, Na⁺, K⁺ have been determined in order to study the chemistry of hoarfrost and rime. Higher total inorganic ionic content (TIC) in hoarfrost and rime (2.46 meq·l⁻¹ and 1.23 meq·l⁻¹ respectively) was observed when compared with precipitation (0.37 meq·l⁻¹). Large variability of TIC and chemical composition of individual samples were typical at each of the measurement sites depending on emission patterns, atmospheric conditions and local terrain topography. Higher concentrations of both hoarfrost and rime occurred in southern (mountainous) rather than in northern (lowland) part of Poland which can be explained by worse pollutant dispersion conditions in the south. The surprisingly low hoarfrost concentrations in urban coastal stations in the area of the Bay of Gdansk were attributed to the cleaning effect of nocturnal breeze-type circulation, best pronounced in cool part of the year. Due to relatively high pollutant concentration and long duration, hoarfrost and rime are at least significant factors in environmental processes in different ecosystems in Poland.     

Kinetics of the reactions of soot surface-bound polycyclic aromatic hydrocarbons with NO<Subscript>2</Subscript>

The kinetics of heterogeneous reactions of NO₂ with 17 polycyclic aromatic hydrocarbons (PAHs) adsorbed on laboratory generated kerosene soot surface was studied over the temperature range (255–330) K in a low pressure flow reactor combined with an electron-impact mass spectrometer. The kinetics of soot-bound PAH consumption due to their desorption and reaction with NO₂ were monitored using off-line HPLC measurements of their concentrations in soot samples as a function of reaction time, NO₂ concentrations in the gas phase being analyzed by mass spectrometer. No measurable decay of PAHs due to the reaction with NO₂ was observed under experimental conditions of the study (maximum NO₂ concentration of 5.5 × 10¹⁴ molecule cm⁻³ and reaction time of 45 min), which allowed to determine the upper limits of the first-order rate constants for the heterogeneous reactions of 17 soot-bound PAHs with NO₂: k < 5.0 × 10⁻⁵ s⁻¹ (for most PAHs studied). Comparison of these results to previous studies carried on different carbonaceous substrates, showed that heterogeneous reactivity of PAHs towards NO₂ is, probably, dependent on the substrate nature even for resembling, although different carbonaceous materials. Results show that particulate PAHs degradation by NO₂ alone is of minor importance in the atmosphere     

Long-term characterization of major water-soluble inorganic ions in PM<Subscript>10</Subscript> in coastal site on the Japan Sea

PM₁₀ samples were collected over three years at Monzenmachi, the Japan Sea coast, the Noto Peninsula, Ishikawa, Japan from January 17, 2001 to December 18, 2003, using a high volume air sampler with quartz filters. The concentrations of the water-soluble inorganic ions in PM₁₀ were determined with using ion chromatography. By analyzing the characteristics of these, the evidences were found that the Asian outflow had an obviously influence on the air quality at our study site. The results were as follows: the secondary pollutants SO₄²⁻, NO₃⁻ and NH₄⁺ were the primary water-soluble inorganic ions at our study site. The monthly mean concentrations of SO₄²⁻, NH₄⁺, NO₃⁻ and Ca²⁺ have prominent peak in spring due to the strong influence of the Asian continent outflow—these according to backward air trajectory analysis, the maximum of which were 6.09 for nss-SO₄²⁻ in May, 2.87 for NO₃⁻ and 0.68 μg m⁻³ for nss-Ca²⁺ in April, respectively. Comparable to similar data reported from various points around East Asia, it had the characteristics of a polluted coastal area at our study site. The concentration of nss-Ca²⁺ in PM₁₀ drastically increased when the Asian dust invaded, the mean value during the Asian dust days(AD) was 0.86 μg m⁻³, about 4 times higher than those of normal days (NAD). Meanwhile, the mean concentrations of nss-SO₄²⁻, NO₃⁻ and NH₄⁺ in AD periods were higher than those in NAD periods which were 5.87, 1.76 and 1.82 μg m⁻³, respectively, it is due to the interaction between dust and secondary particles during the long-range transport of dust storms. Finally, according to the source apportionment with positive matrix factorization (PMF) method in this study, the major source profiles of PM₁₀ at our study site were categorized as (1) marine salt, (2) secondary sulfate, (3) secondary nitrate and (4) crustal source.     

Acid rain and alkalization in southwestern China: chemical and strontium isotope evidence in rainwater from Guiyang

A comprehensive study on the chemical compositions of rainwater was carried out from June 2007 to December 2008 in Guiyang, a city located on the acid rain control zone of southwest China. All samples were analyzed for pH, major anions (F⁻, Cl⁻, NO₃⁻, SO₄²⁻), major cations (K⁺, Na⁺, Ca²⁺, Mg²⁺, NH₄⁺), Sr²⁺ and Sr isotope. The pH increase is due to the result of neutralization caused by the alkaline dust which contain large amount of CaCO₃. It was observed that Ca²⁺ was the most abundant cation with a volume-weighted mean (VWM) value of 217.6 μeq/L (52.7–1928 μeq/L), accounting for 66% (39%–88%) of the total cations. SO₄²⁻ was the most abundant anion with VWM value of 237.8 μeq/L (49.6-1643 μeq/L). SO₄²⁻ and NO₃⁻ were dominant among the anions, accounting for 66%–97% of the total measured anions. The Sr concentrations vary from 0.01 to 0.92 μmol/L, and strontium isotopic ratios vary in the range of 0.707684–0.710094, with an average of 0.708092. The elements ratios and the ⁸⁷Sr/⁸⁶Sr ratios showed that the solutes of rainwater mainly come from weathering of carbonate and secondary dust input. Moreover, urbanization results in the calcium-rich dust increased and the high concentrations of alkaline ions (mainly Ca²⁺) have played an important role to neutralize the acidity of rainwater, leading to the increase of arithmetic pH mean value by 0.5 units since 2002. It is worth noting that the emission of SO₂ and NO_x from the automobile exhaust is increasing and is becoming another important precursor of acid rain now.     

Secondary aerosol formation and identification of regional source locations by PSCF analysis in the Indo-Gangetic region of India

Secondary aerosol formation was studied at Allahabad in the Indo-Gangetic region during a field campaign called Land Campaign-II in December 2004 (northern winter). Regional source locations of the ionic species in PM₁₀ were identified by using Potential Source Contribution Function (PSCF analysis). On an average, the concentration of water soluble inorganic ions (sum of anions and cations) was 63.2 μgm⁻³. Amongst the water soluble ions, average NO₃⁻ concentration was the highest (25.0 μgm⁻³) followed by SO₄²⁻ (15.8 μgm⁻³) and NH₄⁺ (13.8 μgm⁻³) concentrations. These species, contributed 87% of the total mass of water soluble species, indicating that most of the water soluble PM₁₀ was composed of NH₄NO₃ and (NH₄)₂SO₄/NH₄HSO₄ or (NH₄)₃H(SO₄)₂ particles. Further, the concentrations of SO₄²⁻, NO₃⁻, and NH4⁺ aerosols increased at high relative humidity levels up to the deliquescence point (∼63% RH) for salts of these species suggesting that high humidity levels favor the conversion and partitioning of gaseous SO₂, NO_x, and NH₃ to their aerosol phase. Additionally, lowering of ambient temperature as the winter progressed also resulted in an increase of NO₃⁻ and NH₄⁺ concentrations, probably due to the semi volatile nature of ammonium nitrate. PSCF analysis identified regions along the Indo-Gangetic Plain (IGP) including Northern and Central Uttar Pradesh, Punjab, Haryana, Northern Pakistan, and parts of Rajasthan as source regions of airborne nitrate. Similar source regions, along with Northeastern Madhya Pradesh were identified for sulfate.     

Uptake of the NO <Subscript>3</Subscript> Radical on Aqueous Surfaces

Using a single drop experiment, the uptake of NO₃ radicals on aqueous solutions of the dye Alizarin Red S and NaCl was measured at 293 K. Uptake coefficients in the range (1.7–3.1) ⋅ 10^{− 3} were measured on Alizarin Red S solutions. The uptake coefficients measured on NaCl solutions were in the range of (1.1–2.0) ⋅ 10⁻³ depending on the salt concentration. Both experiments lead to a consistent result for the mass accommodation coefficient of α_NO3 = (4.2_{− 1.7}^+2.2)⋅ 10⁻³. The product H(D_l k_Cl−^II)^0.5 for the NO₃ radical was determined to be (1.9 ± 0.2) M atm^{− 1} cm s^−0.5 M^−0.5 s^−0.5 by fitting the uptake data for the NaCl solutions to the so-called resistance model. The yield of the chemical NO₃ radical source was characterized using UV-VIS and FT-IR spectroscopy. The amount of gas-phase NO₃ radicals measured at elevated humidities was less than expected. Instead, a rise of the gas-phase HNO₃ concentration was found indicating a conversion of gas-phase NO₃ radicals to gas-phase HNO₃ on the moist reactor walls.     

A Study of the Reaction of OH Radicals with N-Methyl Pyrrolidinone,N-Methyl Succinimide and N-Formyl Pyrrolidinone

A study of the oxidation mechanism of N-methyl pyrrolidinone (C₅H₉NO, NMP) initiated by hydroxyl radicals was made at EUPHORE at atmospheric pressure (1000 ± 10) mbar of air and ambient temperature (T = 300 ± 5 K). The main products were N-methyl succinimide (NMS) (52 ± 4)% and N-formyl pyrrolidinone (FP) (23 ± 9)%. The relative rate technique was used to determine the rate constants of OH with NMP, NMS and FP, the measured values were (in units of cm³ molecule ^{− 1} s^{− 1}): k_NMP = (2.2 ± 0.4) × 10^{− 11}, k_NMS = (1.4 ± 0.3) × 10^{− 12} and k_FP = (6 ± 1) × 10^{− 12}. The results are presented and discussed in terms of the atmospheric impact.     

Atmospheric inorganic nitrogen in marine aerosol and precipitation and its deposition to the North and South Pacific Oceans

Aerosol and rain samples were collected between 48°N and 55°S during the KH-08-2 and MR08-06 cruises conducted over the North and South Pacific Ocean in 2008 and 2009, to estimate dry and wet deposition fluxes of atmospheric inorganic nitrogen (N). Inorganic N in aerosols was composed of ~68% NH₄⁺ and ~32% NO₃^– (median values for all data), with ~81% and ~45% of each species being present on fine mode aerosol, respectively. Concentrations of NH₄⁺ and NO₃⁻ in rainwater ranged from 1.7–55 μmol L⁻¹ and 0.16–18 μmol L⁻¹, respectively, accounting for ~87% by NH₄⁺ and ~13% by NO₃⁻ of total inorganic N (median values for all data). A significant correlation (r = 0.74, p < 0.05, n = 10) between NH₄⁺ and methanesulfonic acid (MSA) was found in rainwater samples collected over the South Pacific, whereas no significant correlations were found between NH₄⁺ and MSA in rainwater collected over the subarctic (r = 0.42, p > 0.1, n = 6) and subtropical (r = 0.33, p > 0.5, n = 6) western North Pacific, suggesting that emissions of ammonia (NH₃) by marine biological activity from the ocean could become a significant source of NH₄⁺ over the South Pacific. While NO₃⁻ was the dominant inorganic N species in dry deposition, inorganic N supplied to surface waters by wet deposition was predominantly by NH₄⁺ (42–99% of the wet deposition fluxes for total inorganic N). We estimated mean total (dry + wet) deposition fluxes of atmospheric total inorganic N in the Pacific Ocean to be 32–64 μmol m⁻² d⁻¹, with 66–99% of this by wet deposition, indicating that wet deposition plays a more important role in the supply of atmospheric inorganic N than dry deposition.     

Long-term measurements of atmospheric PM<Subscript>2.5</Subscript> and its chemical composition in rural Korea

Long-term measurements of ambient particulate matter less than 2.5 μm in diameter (PM_2.5) and its chemical compositions were performed at a rural site in Korea from December 2005 to August 2009. The average PM_2.5 concentration was 31 μg m⁻³ for the whole sampling period, and showed a slightly downward annual trend. The major components of PM_2.5 were organic carbon, SO₄²⁻, NO₃⁻, and NH₄⁺, which accounted for 55 % of total PM_2.5 mass on average. For the top 10 % of PM_2.5 samples, anionic constituents and trace elements clearly increased while carbonaceous constituents and NH₄⁺ remained relatively constant. Both Asian dust and fog events clearly increased PM_2.5 concentrations, but affected its chemical composition differently. While trace elements significantly increased during Asian dust events, NO₃⁻, NH₄⁺ and Cl were dramatically enhanced during fog events due to the formation of saturated or supersaturated salt solution. The back-trajectory based model, PSCF (Potential Source Contribution Function) identified the major industrial areas in Eastern China as the possible source areas for the high PM_2.5 concentrations at the sampling site. Using factor analysis, soil, combustion processes, non-metal manufacture, and secondary PM_2.5 sources accounted for 77 % of the total explained variance.     

江苏地区二氧化碳浓度时空分布特征分析

利用瓦里关和上甸子大气本底站观测的月平均CO₂浓度数据对GOSAT卫星反演的CO₂浓度数据进行验证,结果表明GOSAT产品与台站观测数据有较好的一致性.利用2009年6月—2011年5月GOSAT反演的CO₂浓度数据,分析了江苏地区CO₂浓度的时空变化特征,结果表明:1)975 hPa高度层CO₂浓度高于850 hPa高度层,CO₂浓度的水平变化要小于垂直变化;2)在季节变化上,CO₂浓度冬季最高,夏季最低,这可能与植被光合作用的强弱变化有关;比较前后两年的CO₂浓度数据,夏季和秋季的增速较快,冬季和春季的增速较慢;3)在日变化上,发现徐州和南京站02时CO₂浓度最高,14时CO₂浓度最低,这可能也与植被光合作用的强弱有关.     

Water interaction with MgCl<Subscript>2</Subscript>×6H<Subscript>2</Subscript>O and NaCl surfaces: measurements of the uptake coefficient

The uptake of water vapor on MgCl₂×6H₂O and NaCl salt dry solid films was studied over the temperature range 240 to 340 K and at 1 Torr pressure of helium using a flow reactor coupled to a modulated molecular beam mass spectrometer. The H₂O to salt uptake data were obtained from the kinetics of H₂O loss on salt coated Pyrex rods. The following Arrhenius expression was obtained for the initial uptake coefficient of H₂O on MgCl₂×6H₂O films: γ ₀ (MgCl₂) = (6.5 ± 1.0) × 10⁻⁶ exp[(470 ± 40)/T] (calculated with specific BET surface area, quoted uncertainties are 1σ statistical). The rate of H₂O adsorption on NaCl was found to be much lower than on MgCl₂×6H₂O, and only an upper limit was determined for the corresponding uptake coefficient: γ (NaCl) ≤ 5.6 × 10⁻⁶ at T = 300 K. The results show that the rate of H₂O adsorption to salt surfaces is drastically dependent on the salt sample composition.     

The Heterogeneous Reaction of NO<Subscript>2</Subscript> with NH<Subscript>4</Subscript>Cl: A Molecular Diffusion Tube Study

The heterogeneous interaction of nitrogen dioxide with ammonium chloride was investigated in a molecular diffusion tube experiment at 295–335 K and interpreted using Monte Carlo trajectory calculations. The surface residence time (τ_surf) of NO₂ on NH₄Cl is equal to 15 μs at 295 K, increases with temperature up to 323 K (τ_surf = 45 μs) and probably decreases beyond 323 K. The same experiment also yields uptake coefficients, γ, which are derived from the absolute number of surviving molecules effusing out of the diffusion tube. The rate of uptake of NO₂ on NH₄Cl followed a rate law first order in [NO₂] and the uptake coefficient γ is equal to 7 × 10⁻⁵ at 295 K, increases with temperature up to 323 K (γ = 2.1 × 10⁻⁴) and probably decreases beyond 323 K. Nitrous acid, water and nitrogen were detected as products. From these products, it is concluded that the reaction of NO₂ with NH₄Cl is a reverse disproportionation reaction where two moles of NO₂ result in ammonium nitrite, NH₄NO₂, as an intermediate, and nitryl chloride, NO₂Cl. NH₄NO₂ decomposes in two pathways, one to nitrous acid, HONO and NH₃, the other to nitrogen and water. The branching ratio for the production of HONO + NH₃ to that of N₂ + H₂O is approximately 20 at 298 K and increases with increasing temperature.