Characteristics of organic and elemental carbon in PM2.5 samples in Shanghai, China

Shanghai is the largest industrial and commercial city in China, and its air quality has been deteriorating for several decades. However, there are scarce researches on the level and seasonal variation of fine particle (PM_2.5) as well as the carbonaceous fractions when compared with other cities in China and around the world. In the present paper, abundance and seasonal characteristics of PM_2.5, organic carbon (OC) and elemental carbon (EC) were studied at urban and suburban sites in Shanghai during four season-representative months in 2005–2006 year. PM_2.5 samples were collected with high-vol samplers and analyzed for OC and EC using thermal-optical transmittance (TOT) protocol. Results showed that the annual average PM_2.5 concentrations were 90.3–95.5 μg/m³ at both sites, while OC and EC were 14.7–17.4 μg/m³ and 2.8–3.0 μg/m³, respectively, with the OC/EC ratios of 5.0–5.6. The carbonaceous levels ranked by the order of Beijing > Guangzhou > Shanghai > Hong Kong. The carbonaceous aerosol accounted for  30% of the PM_2.5 mass. On seasonal average, the highest OC and EC levels occurred during fall, and they were higher than the values in summer by a factor of 2. Strong correlations (r = 0.79–0.93) between OC and EC were found in the four seasons. Average level of secondary organic carbon (SOC) was 5.7–7.2 μg/m³, accounting for  30% of the total OC. Strong seasonal variation was observed for SOC with the highest value during fall, which was about two times the annual average.     

Influence of Transport over a Mountain Ridge on the Chemical Composition of Marine Aerosols during the ACE-2 Hillcloud Experiment

Aerosol chemical composition and trace gas measurements were made at twolocations on the northeastern peninsula of Tenerife during the ACE-2HILLCLOUD experiment, between 28 June and 23 July 1997. Measurementswere made of coarse (#gt;2.5 m aerodynamic diameter) and fine (#lt; 2.5m) aerosol Cl^–, NO₃ ^–,SO₄ ^2–, non-sea saltSO₄ ^2– (NSSS),CH₃SO₃ ^– (MSA) andNH₄ ⁺, and gas phase dimethylsulphide (DMS), HCl,HNO₃, SO₂, CH₃COOH, HCOOH andNH₃. Size distributions were measured using a cascadeimpactor. Results show that in marine air masses NSSS and MSA wereformed via DMS oxidation, with additional NSSS present in air massescontaining a continental component. Using a Eulerian box model approachfor aerosols transported between upwind and downwind sites, a mean NSSSproduction rate of 4.36 × 10^–4 gm^–3 s^–1 was calculated for daytimeclear sky periods (highest insolation), with values for cloudy periodsduring daytime and nighttime of 3.55 × 10^–4 and2.40 × 10^–4 g m^–3s^–1, respectively. The corresponding rates for MSA were6.23 × 10^–6, 8.49 × 10^–6and 6.95 × 10^–6 g m^–3s^–1, respectively. Molar concentration ratios forMSA/NSSS were 8.7% (1.8–18.2%) and 1.9%(1.3–3.5%) in clean and polluted air masses, respectively.Reactions occurring within clouds appeared to have a greater influenceon rates of MSA production, than of NSSS, while conversely daytime gasphase reactions were more important for NSSS. For MSA, nighttimein-cloud oxidation rates exceeded rates of daytime gas phase productionvia OH oxidation of DMS. NSSS, MSA and ammonium had trimodal sizedistributions, with modes at 0.3, 4.0 and >10.0 m (NSSS andNH₄ ⁺), and 0.3, 1.5 and 4.0 m (MSA). Nosignificant production of other aerosol species was observed, with theexception of ammonium, which was formed at variable rates dependent onneutralisation of the aerosol with ammonia released from spatiallynon-uniform surface sources. Seasalt components were mainly present incoarse particles, although sub-micrometre chloride was also measured.Losses by deposition exceeded calculated expectations for all species,and were highest for the seasalt fraction and nitrate.     

Effects of prescribed initial cloud droplet spectra on convective cloud and precipitation developments under different thermodynamic conditions: A modeling and observational study

A two-dimensional cloud model with bin microphysics was used to investigate the effects of cloud condensation nuclei (CCN) concentrations and thermodynamic conditions on convective cloud and precipitation developments. Two different initial cloud droplet spectra were prescribed based on the total CCN concentrations of maritime (300 cm^− 3) and continental (1000 cm^− 3) air masses, and the model was run on eight thermodynamic conditions obtained from observational soundings. Six-hourly sounding data and 1-hourly precipitation data from two nearby weather stations in Korea were analyzed for the year 2002 to provide some observational support for the model results.For one small Convective Available Potential Energy (CAPE) ( 300 J kg^− 1) sounding, the maritime and continental differences were incomparably large. The crucial difference was the production of ice phase hydrometeors in the maritime cloud and only water drops in the continental cloud. Ice phase hydrometeors and intrinsically large cloud drops of the maritime cloud eventually lead to significant precipitation. Meanwhile negligible precipitation developed from the continental cloud. For the three other small CAPE soundings, generally weak convective clouds developed but the maritime and continental clouds were of the same phases (both warm or both cold) and their differences were relatively small.Model runs with the four large CAPE ( 3000 J kg^− 1) soundings demonstrated that the depth between the freezing level (FL) and the lifting condensation level (LCL) was crucial to determine whether a cloud becomes a cold cloud or not, which in turn was found to be a crucial factor to enhance cloud invigoration with the additional supply of freezing latent heat. For two large CAPE soundings, FL–LCL was so deep that penetration of FL was prohibitive, and precipitation was only mild in the maritime clouds and negligible in the continental clouds. Two other soundings of similarly large CAPE had small FL–LCL, and both the maritime and continental clouds became cold clouds. Precipitation was strong for both but much more so in the maritime clouds, while the maximum updraft velocity and the cloud top were slightly higher in continental clouds. Although limited to small CAPE cases, more precipitation for smaller FL–LCL for a selected group of precipitation and thermodynamic sounding data from Korea was in support of these model results in its tendency.These results clearly demonstrated that the CCN effects on cloud and precipitation developments critically depended on the given thermodynamic conditions and not just the CAPE but the entire structure of the thermodynamic profiles had to be taken into account.     

A numerical modeling study of the marine boundary layer over the Gulf Stream during cold air advection

A two-dimensional mesoscale model has been developed to simulate the air flow over the Gulf Stream area where typically large gradients in surface temperature exist in the winter. Numerical simulations show that the magnitude and the maximum height of the mesoscale circulation that develops downwind of the Gulf Stream depends on both the initial geostrophic wind and the large-scale moisture. As expected, a highly convective Planetary Boundary Layer (PBL) develops over this area and it was found that the Gulf Stream plays an important role in generating the strong upward heat fluxes causing a farther seaward penetration as cold air advection takes place. Numerical results agree well with the observed surface fluxes of momentum and heat and the mesoscale variation of vertical velocities obtained using Doppler Radars for a typical cold air outbreak. Precipitation pattern predicted by the numerical model is also in agreement with the observations during the Genesis of Atlantic Lows Experiment (GALE).List of Symbols u east-west velocity [m s^–1] - v north-south velocity [m s^–1] - vertical velocity in coordinate [m s^–1] - w vertical velocity inz coordinate [m s^–1] - gq potential temperature [K] - q moisture [kg kg^–1] - scaled pressure [J kg^–1 K^–1] - U _g the east-south component of geostrophic wind [m s^–1] - V _g the north-south component of geostrophic wind [m s^–1] - vertical coordinate following terrain - x east-west spatial coordinate [m] - y north-south spatial coordinate [m] - z vertical spatial coordinate [m] - t time coordinate [s] - g gravity [m² s^–1] - E terrain height [m] - H total height considered in the model [m] - q _s saturated moisture [kg kg^–1] - p pressure [mb] - p ₀₀ reference pressure [mb] - P precipitation [kg m^–2] - vertical lapse rate for potential temperature [K km^–1] - L latent heat of condensation [J kg^–1] - C _p specific heat at constant pressure [J kg^–1 K^–1] - R gas constant for dry air [J kg^–1 K^–1] - R _v gas constant for water vapor [J kg^–1 K^–1] - f Coriolis parameter (2 sin ) [s^–1] - angular velocity of the earth [s^–1] - latitude [^o] - K _H horizontal eddy exchange coefficient [m² s^–1] - t integration time interval [s] - x grid interval distance inx coordinate [m] - y grid interval distance iny coordinate [m] - adjustable coefficient inK _H - subgrid momentum flux [m² s^–2] - subgrid potential temperature flux [m K s^–1] - subgrid moisture flux [m kg kg^–1 s^–1] - u _* friction velocity [m s^–1] - _* subgrid flux temperature [K] - q _* subgrid flux moisture [kg kg^–1] - w _* subgrid convective velocity [m s^–1] - z ₀ surface roughness [m] - L Monin stability length [m] - _s surface potential temperature [K] - k von Karman's constant (0.4) - v air kinematic viscosity coefficient [m² s^–1] - K _M subgrid vertical eddy exchange coefficient for momentum [m² s^–1] - K subgrid vertical eddy exchange coefficient for heat [m² s^–1] - K _q subgrid vertical eddy exchange coefficient for moisture [m² s^–1] - z _i the height of PBL [m] - h _s the height of surface layer [m]     

Major ionic composition of precipitation in the Nam Co region, Central Tibetan Plateau

A total of 48 precipitation samples have been collected from individual precipitation events at the Nam Co Monitoring and Research Station for Multisphere Interactions (Nam Co Station, 30°47′N, 90°58′E; 4730 m a.s.l) located in the central Tibetan Plateau from August 2005 to August 2006. All samples were analyzed for major cations (NH₄⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺) and anions (Cl⁻, NO₃⁻ and SO₄²⁻), conductivity and pH. Precipitation pH values ranged from 6.03 to 7.38 with an average value of 6.59. The high pH is due to large inputs of crustal aerosols in the atmosphere, which contain a large fraction of carbonate. Ca²⁺ is the dominant cation in precipitation with an average value of 65.58 μeq L^− 1 (4.91–301.41 μeq L^− 1), accounting for 54% of the total cations in precipitation. HCO₃⁻ is the predominant anion, accounting for 62% of the total anions. When compared with data from a snow pit in the Zhadang Glacier 50 km away (5800 m a.s.l), major ion concentration in precipitation at the Nam Co Station is much higher due to local aerosol inputs. Correlation and empirical orthogonal function (EOF) analysis indicate that regional crustal aerosols and species from combustion emissions of residents are the major sources for these ions, lake salt aerosols from the Nam Co nearby and regional mineral aerosols from dry lake sediments are secondary sources, and sea salt contribution is the least due to the long distance transport.     

Concentration of Peroxides and Formaldehyde in Air and Rain and Gas-Rain Partitioning

Rain and air of Florence have been collected in a continuous way andanalysed by flow analysis spectrofluorimetric methods for formaldehydeand hydrogen peroxide. Diurnal and seasonal variations were observed;the mean/maximum concentrations of all data (as gm^–3) are 3.3/23.4 for HCHO and 0.4/4.93 forH₂O₂. The effect of external sources and ofphotochemical reactions produces periods of positive and negativecorrelations for these compounds. The mean/maximum rain concentration ofall data are 98/443 g l^–1 for HCHO and 84/685 g l^–1 for H₂O₂. Concentrationratios rain/air and discrepancies to Henry's Law equilibrium arediscussed.     

Prediction of the abiotic degradability of organic compounds in the troposphere

A statistically relevant correlation between the reaction rate coefficient, k _OH, for the OH radical reaction with 161 organic compounds in the gas phase at 300 K, and the corresponding vertical ionisation energies E _i,v, reveals two classes of compounds: aromatics where –log(k _OH/cm³s^-1)3/2E _i,v(eV)–2 and aliphatics where –log(k _OH/cm³s^-1)4/5E _i,v(eV)+3. The prediction of the rate coefficient, k _OH, for the reaction of OH with organic molecules from the above equations has a probability of about 90%. Assuming a global diurnal mean of the OH radical concentration of 5×10⁵ cm³, the upper limit of the tropospheric half-life of organic compounds and their persistence can be estimated.     

Gamma Emitters on Micro-Becquerel Activity Level in Air at Kraków (Poland)

The Petryanov air filters combined into half-year sets were analyzed for the presence of ⁴⁰K, ¹³⁷Cs and ²²Na by means of low-background gamma rays spectrometry. Each sample contains aerosols from more than 1 Mm³ of air. Samples were collected in ground level air at Kraków (Southern Poland) from 1996 to 2002. Activity concentrations of ⁴⁰K are almost constant with the mean of 14.7± 4.5 Bq m^–3. Activity concentrations of ¹³⁷Cs, which are on the level of single Bq m^{– 3} show exponential decrease with effective half-life time of 7.07± 0.77 years. The cosmogenic ²²Na shows a strong seasonal variation with significant different mean values activity concentration between 0.333± 0.095 Bq m^–3 and 0.137± 0.045 Bq m^–3, for summer and winter, respectively. Moreover, the activity ratio for two cosmogenic radionuclides: ²²Na and measured previously ⁷Be show also changes with statistically significant seasonal differences. The lower values were found during winters. The mechanisms which might govern this ratio are discussed. The conclusion is that transport of ²²Na during summer seems to be so much effective, that results in kind of relative depletion of stratosphere of this nuclide.     

The prediction of dust erosion by wind: An interactive model

We have devised a partial differential equation for the prediction of dust concentration in a thin layer near the ground. In this equation, erosion (detachment), transport, deposition and source are parameterised in terms of known quantities. The interaction between a wind prediction model in the boundary layer and this equation affects the evolution of the dust concentration at the top of the surface layer. Numerical integrations are carried out for various values of source strength, ambient wind and particle size. Comparison with available data shows that the results appear very reasonable and that the model should be subjected to further development and testing.Notation (x, y, z, t) space co-ordinates and time (cm,t) - u, v components of horizontal wind speed (cm s^–1) - u _g, v_g components of the geostrophic wind (cm s^–1) - V=(u²+v²)^1/2 (cm s^–1) - (û v)= 1/(h – k) _k ^h(u, v)dz(cm s^–1) - V _* friction velocity (cm s^–1) - z ₀ roughness length (cm) - k ₁ von Karman constant =0.4 - V _d deposition velocity (cm s^–1) - V _g gravitational settling velocity (cm s^–1) - h height of inversion (cm) - k height of surface layer (cm) - potential temperature (°K) - _gr potential temperature at ground (°K) - _K potential temperature at top of surface layer (°K) - P pressure (mb) - P ₀ sfc pressure (mb) - C _p/C_v - (t)= /z lapse rate of potential temperature (°K cm^–1) - A(z) variation of wind with height in transition layer - B(z) variation of wind with height in transition layer - Cd drag coefficient - C _HO transfer coefficient for sensible heat - C dust concentration (g m^–3) - C _K dust concentration at top of surface layer (g m^–3) - D(z) variation with height of dust concentration - u, v, w turbulent fluctuations of the three velocity components (cm s^–1) - A ₁ constant coefficient of proportionality for heat flux =0.2 - Ri Richardson number - g gravitational acceleration =980 cm s^–2 - Re Reynolds number = - D _s thickness of laminar sub-layer (cm) - v molecular kinematic viscosity of air - coefficient of proportionality in source term - dummy variable - t time step (sec) - n time index in numerical equations On sabbatical leave at University of Aberdeen, Department of Engineering, September 1989–February 1990.     

Instabilities of the tidally induced bottom boundary layer in the rotating frame and their mixing effect

To investigate the stability of the bottom boundary layer induced by tidal flow (oscillating flow) in a rotating frame, numerical experiments have been carried out with a two-dimensional non-hydrostatic model. Under homogeneous conditions three types of instability are found depending on the temporal Rossby number Ro_t, the ratio of the inertial and tidal periods. When Ro_t < 0.9 (subinertial range), the Ekman type I instability occurs because the effect of rotation is dominant though the flow becomes more stable than the steady Ekman flow with increasing Ro_t. When Ro_t > 1.1 (superinertial range), the Stokes layer instability is excited as in the absence of rotation. When 0.9 < Ro_t < 1.1 (near-inertial range), the Ekman type I or type II instability appears as in the steady Ekman layer. Being much thickened (100 m), the boundary layer becomes unstable even if tidal flow is weak (5 cm/s). The large vertical scale enhances the contribution of the Coriolis effect to destabilization, so that the type II instability tends to appear when Ro_t > 1.0. However, when Ro_t < 1.0, the type I instability rather than the type II instability appears because the downward phase change of tidal flow acts to suppress the latter. To evaluate the mixing effect of these instabilities, some experiments have been executed under a weak stratification peculiar to polar oceans (the buoyancy frequency N²  10⁻⁶ s⁻²). Strong mixing occurs in the subinertial and near-inertial ranges such that tracer is well mixed in the boundary layer and an apparent diffusivity there is evaluated at 150–300 cm²/s. This suggests that effective mixing due to these instabilities may play an important role in determining the properties of dense shelf water in the polar regions.     

Vertical distribution of dimethylsulfide,sulfur dioxide,aerosol ions,and radon over the Northeast Pacific Ocean

Dimethylsulfide (DMS), sulfur dioxide (SO₂), methanesulfonate (MSA), nonsea-salt sulfate (nss-SO₄ ^2–), sodium (Na⁺), ammonium (NH₄ ⁺), and nitrate (NO₃ ^–) were determined in samples collected by aircraft over the open ocean in postfrontal maritime air masses off the northwest coast of the United States (3–12 May 1985). Measurements of radon daughter concentrations and isentropic trajectory calculations suggested that these air masses had been over the Pacific for 4–8 days since leaving the Asian continent. The DMS and MSA profiles showed very similar structures, with typical concentrations of 0.3–1.2 and 0.25–0.31 nmol m^–3 (STP) respectively in the mixed layer, decreasing to 0.01–0.12 and 0.03–0.13 nmol m^–3 (STP) at 3.6 km. These low atmospheric DMS concentrations are consistent with low levels of DMS measured in the surface waters of the northeastern Pacific during the study period.The atmospheric SO₂ concentrations always increased with altitude from <0.16–0.25 to 0.44–1.31 nmol m^–3 (STP). The nonsea-salt sulfate (ns-SO₄ ^2–) concentrations decreased with altitude in the boundary layer and increased again in the free troposphere. These data suggest that, at least under the conditions prevailing during our flights, the production of SO₂ and nss-SO₄ ^2– from DMS oxidation was significant only within the boundary layer and that transport from Asia dominated the sulfur cycle in the free troposphere. The existence of a sea-salt inversion layer was reflected in the profiles of those aerosol components, e.g., Na⁺ and NO₃ ^–, which were predominantly present as coarse particles. Our results show that long-range transport at mid-tropospheric levels plays an important role in determining the chemical composition of the atmosphere even in apparently remote northern hemispheric regions.     

Short-Term Variability of Atmospheric DMS and Its Oxidation Products at Amsterdam Island during Summer Time

A one-month experiment was performed at Amsterdam Island in January 1998, to investigate the factors controlling the short-term variations of atmospheric dimethylsulfide (DMS) and its oxidation products in the mid-latitudes remote marine atmosphere. High mixing ratios of DMS, sulfur dioxide (SO₂) and dimethylsulfoxide (DMSO) have been observed during this experiment, with mean concentrations of 395 parts per trillion by volume (pptv) (standard deviation, = 285, n = 500), 114 pptv ( = 125, n = 12) and 3 pptv ( = 1.2, n = 167), respectively. Wind speed and direction were identified as the major factors controlling atmospheric DMS levels. Changes in air temperature/air masses origin were found to strongly influence the dimethylsulfoxide (DMSO)/DMS and SO₂/DMS molar ratios, in line with recent laboratory data. Methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^2–) mean concentrations in aerosols during this experiment were 12.2± 6.5 pptv (1, n=47) and 59 ± 33 pptv (1, n=47), respectively. Evidence of vertical entrainment was reported following frontal passages, with injection of moisture-poor, ozone-rich air. High MSA/ nss-SO₄ ^2– molar ratios (mean 0.44) were calculated during these events. Finally following frontal passages, few spots in condensation nuclei (CN) concentration were also observed.     

Analysis of rainfall characteristics of the Madden–Julian oscillation using TRMM satellite data

Rainfall characteristics of the Madden–Julian oscillation (MJO) are analyzed primarily using tropical rainfall measuring mission (TRMM) precipitation radar (PR), TRMM microwave imager (TMI) and lighting imaging sensor (LIS) data. Latent heating structure is also examined using latent heating data estimated with the spectral latent heating (SLH) algorithm.The zonal structure, time evolution, and characteristic stages of the MJO precipitation system are described. Stratiform rain fraction increases with the cloud activity, and the amplitude of stratiform rain variation associated with the MJO is larger than that of convective rain by a factor of 1.7. Maximum peaks of both convective rain and stratiform rain precede the minimum peak of the outgoing longwave radiation (OLR) anomaly which is often used as a proxy for the MJO convection. Stratiform rain remains longer than convective rain until 4000 km behind the peak of the mature phase. The stratiform rain contribution results in the top-heavy heating profile of the MJO.Associated with the MJO, there are tri-pole convective rain top heights (RTH) at 10–11, 7 and 3 km, corresponding to the dominance of afternoon showers, organized systems, and shallow convections, respectively. The stratiform rain is basically organized with convective rain, having similar but slightly lower RTH and slightly lags the convective rain maximum. It is notable that relatively moderate (7 km) RTH is dominant in the mature phase of the MJO, while very tall rainfall with RTH over 10 km and lightning frequency increase in the suppressed phase. The rain-yield-per flash (RPF) varies about 20–100% of the mean value of 2–10 × 10⁹ kg fl⁻¹ over the tropical warm ocean and that of 2–5 × 10⁹ kg fl⁻¹ over the equatorial Islands, between the convectively suppressed phase and the active phase of MJO, in the manner that RPF is smaller in the suppressed phase and larger in the active phase.     

Seasonal variation of PM10-bound PAHs in the atmosphere of Xiamen, China

PM₁₀ samples from a garden site (site A), an industrial-traffic intersection (site B), a residential site (site C) and an island site (site D) were collected at December 21–29, 2004; March 18–22, 2005; July 4–13, 2005 and October 24–28, 2005 in Xiamen. 15 priority PAHs compounds were analyzed by using a gas chromatograph/mass spectrometer (GC/MS). The abundance and origin of PAHs are discussed to reveal seasonal variations in Xiamen air quality. Average concentrations of Σ15PAHs were 17.5 ng/m³, 3.7 ng/m³, 32.6 ng/m³ and 10.5 ng/m³ from spring to winter with the highest value in autumn. The dominant PAHs components in every season were low and middle molecular weight PAHs including phenanthrene, pyrene, fluoranthene and chrysene. Diagnostic ratios and PCA analysis identified the main sources of particle bound PAHs: mainly from both gasoline and diesel vehicles exhaust, with some contribution from coal combustion, industry emission and cooking sources.     

Study of small ions concentration in the air above Athens, Greece

Measurements of positive and negative small atmospheric ion concentrations have been made regularly since 1968 at the National Observatory of Athens (NOA). In this paper the 17-year period 1968–1984 is summarized. The diurnal and annual variations are examined, and Fourier analysis is also used for the study of the diurnal variation. The concentrations of small ions follow a double diurnal course. The maxima occur near 3–5 h and 13–16 h local time (LT = GMT + 2 h). The minima are observed at 6–8 h and 21–23 h. The annual course of small ions presents maximum concentration values around the summer season. The mean of the small ion concentration (SIC) for the 17-year period (1968–1984) is n₊ = 188.8 ions/cm³ for positive ions and n₋ = 151.1 ions/cm³ for negative ions. Their ratio is equal to 1.25. The year-to-year variation of SIC for the examined period shows a negative trend. The results from multiple regression analysis show that wind speed and SIC are positively correlated, while relative humidity, smoke and sulphur dioxide are negatively correlated.     

Sulfur dioxide plume dispersion and subsequent absorption by coniferous forests: Field measurements and model calculations

A Forest SO₂ Absorption Model (ForSAM) was developed to simulate (1) SO₂ plume dispersion from an emission source, (2) subsequent SO₂ absorption by coniferous forests growing downwind from the source. There are three modules: (1) a buoyancy module, (2) a dispersion module, and (3) a foliar absorption module. These modules were used to calculate hourly abovecanopy SO₂ concentrations and in-canopy deposition velocities, as well as daily amounts of SO₂ absorbed by the forest canopy for downwind distances to 42 km. Model performance testing was done with meteorological data (including ambient SO₂ concentrations) collected at various locations downwind from a coal-burning power generator at Grand Lake in central New Brunswick, Canada. Annual SO₂ emissions from this facility amounted to about 30,000 tonnes. Calculated SO₂ concentrations were similar to those obtained in the field. Calculated SO₂ deposition velocities generally agreed with published values.Notation c air parcel cooling parameter (non-dimensional) - E foliar absorption quotient (non-dimensional) - f areal fraction of foliage free from water (non-dimensional) - f _w SO₂ content of air parcel - h height of the surface layer (m) - H height of the convective mixing layer (m) - H _stack stack height (m) - k time level - k _drag coefficient of drag on the air parcel (non-dimensional) - K _z eddy viscosity coefficient for SO₂ (m²·s^–1) - L Monin-Obukhov length scale (m) - L _A single-sided leaf area index (LAI) - n degree-of-sky cloudiness (non-dimensional) - N number of parcels released with every puff (non-dimensional) - PAR photosynthetically active radiation (W m^–2) - Q emission rate (kg s^–2) - r _b diffusive boundary-layer resistance (s m^–1) - r _c canopy resistance (s m^–1) - r _cuticle cuticular resistance (s m^–1) - r _m mesophyllic resistance (s m^–1) - r _s stomatal resistance (s m^–1) - r _exit smokestack exit radius (m) - R normally distributed random variable with mean of zero and variance of t (s) - u _* frictional velocity scale, (m s^–1) - v lateral wind vector (m s^–1) - v _d SO₂ dry deposition velocity (m s^–1) - VCD water vapour deficit (mb) - z _can mean tree height (m) - Z zenith position of the sun (deg) - environmental lapse rate (°C m^–1) - dry adiabatic lapse rate (0.00986°C m^–1) - von Kármán's constant (0.04) - _B vertical velocities initiated by buoyancy (m s^–1) - canopy extinction coefficient (non-dimensional) - ()a denotes ambient conditions - ()can denotes conditions at the top of the forest canopy - ()h denotes conditions at the top of the surface layer - ()H denotes conditions at the top of the mixed layer - ()s denotes conditions at the canopy surface - ()p denotes conditions of the air parcels     

Solubilities of pyruvic acid and the lower (C1-C6) carboxylic acids. Experimental determination of equilibrium vapour pressures above pure aqueous and salt solutions

Henry's law constantsK _H (mol kg^–1 atm^–1) have been determined at 298.15 K for the following organic acids: formic acid (5.53±0.27×10³); acetic acid (5.50±0.29×10³); propionic acid (5.71±0.34×10³);n-butyric acid (4.73±0.18×10³); isobutyric acid (1.13±0.12×10³); isovaleric acid (1.20±0.11×10³) and neovaleric acid (0.353±0.04×10³). They have also been determined fromT=278.15 K toT=308.15 K forn-valeric acid (ln(K _H)=–14.3371+6582.96/T);n-caproic acid (ln(K _H)=–13.9424+6303.73/T) and pyruvic acid (ln(K _H)=–4.41706+5087.92/T). The influence of 9 salts on the solubility of pyruvic acid at 298.15 K has been measured. Pyruvic acid is soluble enough to partition strongly into aqueous atmospheric aerosols. Other acids require around 1 g of liquid water m^–3 (typical of clouds) to partition significantly into the aqueous phase. The degree of partitioning is sensitive to temperature. Considering solubility and dissociation (to formate) alone, the ratio of formic acid to acetic acid in liquid water in the atmosphere (at equilibrium with the gas phase acids) is expected to increase with rising pH, but show little variation with temperature.     

Characteristics of biomass burning aerosol and its impact on regional air quality in the summer of 2003 at Gwangju, Korea

The main objective of this study is to investigate the chemical characteristics of biomass burning aerosol and its impact on regional air quality during an agricultural waste burning period in early summer in the rural areas of Korea. A 12-h integrated intensive sampling of biomass burning aerosol in the fine and coarse modes was conducted on 2–20 June 2003 in Gwangju, Korea. The collected samples were analyzed for concentrations of mass, ionic, elemental, and carbonaceous species. Average concentrations of fine and coarse mass were measured to be 67.9 and 18.7 μg m^− 3 during the biomass burning period, 41.9 and 18.8 μg m^− 3 during the haze period, and 35.6 and 13.3 μg m^− 3 during the normal period, respectively. An exceptionally high PM_2.5 concentration of 110.3 μg m^− 3 with a PM_2.5/PM₁₀ ratio of 0.79 was observed on 6 June 2003 during the biomass burning period. The potassium ratio method was used to identify biomass burning samples. The average ratio of potassium in the fine mode to the coarse mode (FK/CK) was 23.8 during the biomass burning period, 6.0 during the haze period, and 4.7 during the normal period, respectively. A FK/CK ratio above 9.2 was considered a criterion for biomass burning event in this study. Particulate matter from the open field burning of agricultural waste has an adverse impact on visibility, human health, and regional air quality.     

The role of gravitophotophoresis for stratospheric and mesospheric particulates

Gravitophotophoresis, a type of photophoresis related to the direction of gravity, is examined in view of its possible importance to some aerosols in stratosphere and mesosphere. particles of various materials from about 1 to 100 m in size show levitation by photophoretic forces under laboratory simulation of irradiation by the sun at air densities of the middle atmosphere. Minimum air densities for levitation are about 2–3 g m^–3 with mineral and metallic powders, about 0.08 g m^–3 with carbonaceous powders. The fraction of rising particles can be about 0.01 to 1%. Velocities of ascent are in the range of 0.001 to 0.01 m s^–1 at a pressure of several mbar. The magnitude and the mechanical character of the force of gravitophotophoresis can be explained if it is identified with a radiometer force caused by a difference of the accommodation coefficient on the surface. It is suggested that gravitophotophoresis can be important to the residence time and the maximum altitude of carbonaceous and mineral particles, such as volcanic ash or products of meteorite impact, and to the presence of microorgnisms in the middle atmosphere.     

Environmental aerosols and their effect on the Earth’s local fair-weather electric field

Summary The Earths local fair-weather electric field is significantly affected by small ions present in the atmosphere. These ions are typically smaller than 0.001µm and occur in concentrations from 500 to 600cm^–3 in air. Attachment to larger aerosol particles may severely decrease the mobility of these atmospheric ions resulting in an increased local electric field. The number concentration of environmental aerosol particles in the size range 0.1 to 5.0µm was measured with two automatic laser scattering particle counters. The Earths electric field was monitored with an electric fieldmeter. Measurements were made in clean air and in an environment highly polluted by wood smoke. The electric field was found to be positively correlated to the aerosol number concentration. During one 24-hour period of measurement, the electric field increased from 180 to about 280Vm^–1 as the number concentration of aerosols larger than 0.1µm increased from about 2000 to 9000cm^–3. The number concentrations of aerosols larger than 0.1 and 0.3µm were both found to be positively correlated with the Earths electric field with correlation coefficients of 70% and 61%, respectively.Present address: School of Physical Sciences, Queensland University of Technology, Brisbane 4001, Australia.