Meteorology and haze structure during AGASP-II,Part 1: Alaskan Arctic flights, 2–10 April 1986

The second Arctic Gas and Aerosol Sampling Program (AGASP-II) was conducted across the Alaskan and Canadian Arctic in April 1986, to study the in situ aerosol, and the chemical and optical properties of Arctic haze. The NOAA WP-3D aircraft, with special instrumentation added, made six flights during AGASP-II. Measurements of wind, pressure, temperature, ozone, water vapor, condensation nuclei (CN) concentration, and aerosol scattering extinction (b_sp) were used to determine the location of significant haze layers. The measurements made on the first three flights, over the Arctic Ocean north of Barrow and over the Beaufort Sea north of Barter Island, Alaska are discussed in detail in this report of the first phase of AGASP II. In the Alaskan Arctic the WP-3D detected a large and persistent region of haze between 960 and 750 mb, in a thermally stable layer, on 2, 8, and 9 April 1986. At its most dense, the haze contained CN concentrations >10,000 cm^–3 and b_sp of 80×10^–6 m^–1 suggesting active SO₂ to H₂SO₄ gas-to-particle conversion. Calculations based upon observed SO₂ concentrations and ambient relative humidities suggest that 10⁴–10⁵ small H₂SO₄ droplets could have been produced in the haze layers. High concentrations of sub-micron H₂SO₄ droplets were collected in haze. Ozone concentrations were 5–10 ppb higher in the haze layers than in the surrounding troposphere. Outside the regions of haze, CN concentrations ranged from 100 to 400 cm^–3 and b_sp values were about (20–40)×10^–6 m^–1. Air mass trajectories were computed to depict the air flow upwind of regions in which haze was observed. In two cases the back trajectories and ground measurements suggested the source to be in central Europe.     

The solubility of SO2 and the dissociation of H2SO3 in NaCl solutions

The pK ₁ ^* and pK ₂ ^* of H₂SO₃ have been determined in NaCl solutions as a function of ionic strength (0.1 to 6 m) and temperature (5 and 25 °C). The extrapolated values in water were found to be in good agreement with literature data. The experimental results have been used to determine the Pitzer interaction parameters for SO₂, HSO ₃ ^- and SO ₃ ^- in NaCl solutions. The resultant parameters for NaHSO₃ and Na₂SO₃ were found to be in reasonable agreement with the values for NaHSO₄ and Na₂SO₄. It, thus, seems reasonable to assume that the interactions of Mg²⁺ and Ca²⁺ with HSO ₃ ^- and SO ₃ ^- can be estimated from the values with HSO ₄ ^- and SO ₄ ^- until experimental values are available. Measurements of pK ₁ ^* and pK ₂ ^* in artificial seawater were found to be in good agreement with the calculated values using the derived Pitzer parameters. It is, thus, possible to make reasonable estimates of the activity coefficients of HSO ₃ ^- and SO ₃ ^- ions and pK ₁ ^* and pK ₂ ^* for the ionization of H₂SO₃ in marine aerosols.     

Shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide in the Caribbean and Gulf of Mexico

Simultaneous shipboard measurements of atmospheric dimethylsulfide and hydrogen sulfide were made on three cruises in the Gulf of Mexico and the Caribbean. The cruise tracks include both oligotrophic and coastal waters and the air masses sampled include both remote marine air and air masses heavily influenced by terrestrial or coastal inputs. Using samples from two north-south Caribbean transects which are thought to represent remote subtropical Atlantic air, mean concentrations of DMS and H₂S were found to be 57 pptv (74 ng S m^-3, =29 pptv, n=48) and 8.5 pptv (11 ng S m^-3, =5.3 pptv, n=36), respectively. The ranges of measured concentrations for all samples were 0–800 pptv DMS and 0–260 pptv H₂S. Elevated concentrations were found in coastal regions and over some shallow waters. Statistical analysis reveals slight nighttime maxima in the concentrations of both DMS and H₂S in the remote marine atmosphere. The diurnal nature of the H₂S data is only apparent after correcting the measurements for interference due to carbonyl sulfide. Calculations using the measured ratio of H₂S to DMS in remote marine air suggest that the oxidation of H₂S contributes only about 11% to the excess (non-seasalt) sulfate in the marine boundary layer.     

Solubility of HOCl in water and aqueous H2SO4 to stratospheric temperatures

Henry's law constants K_H (mol kg^–1 atm^–1) for the reaction HOCl_(g)=HOCl_(aq) near room temperature, literature data for the associated enthalpy change, and solubilities of HOCl in aqueous H₂SO₄ (46 to 60 wt%) at temperatures relevant to the stratosphere (200 KT230 K) are shown to be thermodynamically consistent. Effective Henry's law constants [H*=mHOCl/pHOCl, in mol kg^–1 atm^–1] of HOCl in aqueous H₂SO₄ are given by: ln(H*)=6.4946–mH₂SO₄(–0.04107+54.56/T)–5862 (1/T_o–1/T) where T(K) is temperature and T_o=298.15K. The activity coefficient of HOCl in aqueous H₂SO₄ has a simple Setchenow-type dependence upon H₂SO₄ molality.     

The influence of light intensity,SO2, NOx and C3H6 on sulfate aerosol formation

The photochemical oxidation of SO₂ in the presence of NO and C₃H₆ was studied in a 18.2 liter pyrex reactor. When light intensity, irradiation time and SO₂ concentration were constant, SO₄ ^2- concentration, derived from the total volume of aerosol produced, peaked when [C₃H₆]/[NO] was approximately 6.0. Another increase im SO₄ ^2- formation was reached at very high ratios (>50). The experimental observations are consistent with the two SO₂ oxidation mechanisms. At low [C₃H₆]/[NO] ratios, the processes proceed via the HO–SO₂ reaction, while at high ratios the O₃–C₃H₆ adduct is assumed to oxidize SO₂ to produce SO₄ ^2- aerosols.     

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide,hydrogen sulphide,aliphatic thiols and thiophenol

The reactions of OH radicals with SO₂, H₂S, thiophenol, and a series of aliphatic thiols (1–5 C-atoms) have been investigated in 201 and 381 reaction chambers at 1 atm total pressure and 300 K using a competitive kinetic technique. Initially, OH radicals were produced by photolysis of CH₃ONO/NO mixtures in air. Applying this OH source rate constants for OH with SO₂, H₂S, and thiophenol in synthetic air were determined to be (1.1±0.2)×10^-12, (5.5±0.8)×10^-12 and (1.1±0.2)×10^-11 cm³ s^-1, respectively. However, when this method was applied to the aliphatic thiols the rate constants obtained were found to be dependent on the partial pressures of O₂ and NO. These effects have been attributed to the built-up of a radical species, not yet identified, which leads to uncontrolled chain reactions in the system. Using the photolysis of H₂O₂ at wavelengths greater than 260 nm as the OH source in 1 atm N₂, rate constants for the 1–5 aliphatic thiols in the range 2.9 to 5.6×10^-11 cm³ s^-1 were obtained. The rate constants obtained in the present study are compared with recent literature values.     

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     

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.     

Biogenic hydrogen sulphide emissions and non-sea sulfate aerosols over the Indian Sundarban mangrove forest

Temporal variations in atmospheric hydrogen sulphide concentrations and its biosphere-atmosphere exchanges were studied in the World’s largest mangrove ecosystem, Sundarbans, India. The results were used to understand the possible contribution of H₂S fluxes in the formation of atmospheric aerosol of different size classes (e.g. accumulation, nucleation and coarse mode). The mixing ratio of hydrogen sulphide (H₂S) over the Sundarban mangrove atmosphere was found maximum during the post-monsoon season (October to January) with a mean value of 0.59?±?0.02 ppb and the minimum during pre-monsoon (February to May) with a mean value of 0.26?±?0.01 ppb. This forest acted as a perennial source of H₂S and the sediment-air emission flux ranged between 1213?±?276 μg S m^?2 d^?1(December) and 457?±?114 μg S m^?2 d^?1 (August) with an annual mean of 768?±?240 μg S m^?2d^?1. The total annual emissions of H₂S from the Indian Sundarban were estimated to be 1.2?±?0.6 Tg S. The accumulation mode of aerosols was found to be more enriched with non-sea salt sulfate with an average loading of 5.74 μg m^?3 followed by the coarse mode (5.18 μg m^?3) and nucleation mode (1.18 μg m^?3). However, the relative contribution of Non-sea salt sulfate aerosol to total sulfate aerosol was highest in the nucleation mode (83%) followed by the accumulation (73%) and coarse mode (58%). Significant positive relations between H₂S flux and different modes of NSS indicated the likely link between H₂S, a dominant precursor for the non-sea salt sulfate, and non-sea sulfate aerosol particles. An increase in H₂S emissions from the mangrove could result in an increase in enhanced NSS in aerosol and associated cloud albedo, and a decrease in the amount of incoming solar radiation reaching the Sundarban mangrove forest.     

Field study of dimethylsulfide oxibation in the boundary layer: Variations of dimethylsulfide,methanesulfonic acid,sulfur dioxide,non-sea-salt sulfate and aitken nuclei at a coastal site

Measurements of atmospheric dimethylsulfide (DMS) and its oxidation products, sulfur dioxide (SO₂), methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^2-) were monitored during the period June 9–26, 1989 at a coastal site in Brittany. As indicated by the radon (Rn-222) activities and the high concentrations of NOx the air masses, for most of the experiment, were continental in origin. The observed concentrations range from 1.9 to 65 nmol/m³ for DMS (n=157), 0.6 to 94.2 nmol/m³ for SO₂ (n=50), 0.6 to 11.6 nmol/m³ for MSA (n=44) and 42 to 350 nmol/m³ for nss-SO₄ ^2- (n=44). Aitken nuclei reached values as high as 4.5 × 10⁵ particles/m³. When continental conditions predominated, the measured SO₂ concentrations were lower than those expected from a consideration of the observed DMS concentrations and the existence of SO₂ background of the continental air masses. Similarly, compared to the MSA/DMS ratio in the marine atmosphere, higher concentrations of MSA were observed than those expected from the measured levels of DMS. The presence of enhanced levels of MSA was also endorsed by the observation that the measured mean MSA/nss-SO₄ ^2- ratio of 6±3% was similar to the mean value of 6.9% observed in the marine atmosphere. These above observations are in line with recent laboratory findings by Barnes et al. (1988), which show an increase of the MSA/DMS yield with a simultaneous decrease of the SO₂/DMS yield in the presence of NOx.     

Observation of Filterable Bromine Variabilities During Arctic Tropospheric Ozone Depletion Events in High (1hour) Time Resolution

The halogen ions Br^- and Cl^- together with NO₃ ^-, SO₄ ⁼, MSA^- (methane sulfonate), Na⁺ and NH₄ ⁺ were analysed by ion chromatography in extracts of more than 800 aerosol cellulose filter samples taken at Ny Ålesund, Svalbard (79°N, 12°E) in spring 1996 (March 27 - May 16) within the European Union project ARCTOC (Arctic Tropospheric Ozone Chemistry). Anticorrelated variations between f-Br (filterable bromine, i.e. water soluble bromine species that can be collected by aerosol filters) and ozone within the arctic troposphere were evaluated at a resolution of 1 or 2 hours for periods with depleted ozone and 4 hours at normal ozone. A mean f-Br concentration of 11 ng m^-3 (0.14 nmol m^-3) was observed for the whole campaign, while maximum concentrations of 80 ng m^-3 (1 nmol m^-3) were detected during two total O₃-depletion events (O₃ drop to mixing ratios below the detection limit of < 2 ppb). Anticorrelation between f-Br and O₃ was also seen during minor O₃-depletion episodes (sudden drop in O₃ by at least 10 ppb, but O₃ still exceeding the detection limit) and even for ozone variations near its background level (40-50 ppb). A time lag of about 10 hours between the change of ozone and of f-Br concentrations could only be found during a total ozone depletion event, when f-Br reached its maximum values several hours after ozone was totally destroyed. Bromine oxide (BrO) concentrations, measured by DOAS (Differential Optical Absorption Spectroscopy), and f-Br showed a coincident variability during almost the entire campaign (except in the case of total O₃-loss). Frequently enhanced anthropogenic nitrate and sulphate concentrations were observed during O₃-depletion periods. At O₃ concentrations < 10 ppb sulphate and nitrate exceed their typical mean level by 54% and 77%, respectively. This may indicate a possible connection between acidity and halogen release.     

Rapid change in nitrate and sulfate concentrations observed in early stage of precipitation and their deposition processes

The concentrations of H⁺, nitrate (NO₃ ^-), and sulfate (SO₄ ^2-) in rainwater and their temporal changes were analyzed on the basis of continuous observation from 1 July 1991 to 30 June 1992 at a suburb of Nagoya, Japan. The yearly average for pH was 4.4. In general, an increasing pH with increase in precipitation amount was observed for rain events. Relatively high pH rainwater was sometimes observed at the beginning of rainfall, even though high concentrations of NO₃ ^- and SO₄ ^2- were involved. The high pH values were considered to be caused by the neutralization process with particulate matter containing cations. The yearly averaged ratio of equivalent concentration of nitrate to sulfate (N/S) in rainwater was 0.58. In the early stage of rain, the N/S value was usually more than 1.0 due to the difference of scavenging process between NO₃ ^- and SO₄ ^2-. High values of N/S ranging from 5 to 10 were found under the atmospheric conditions of calm winds and low humidity, during which it is possible that atmospheric particles float for a long time in the air before a rain event. The adsorption of NO₃ ^- in the early stage of rainfall by particulate matter was suggested from the difference in scavenging processes of NO₃ ^- and SO₄ ^2-. A possible scavenging process, called limb cloud scavenging, is presented to explain the interaction of particles and nitrate ions at the early stage of rain. In limb cloud scavenging, the repeated migration of cloud particles or raindrops between the inside and outside of clouds increases the absorption of ions to a highly condensed level, thus increasing the N/S value of rainwater. The influence of global scale seasonal phenomena with large amounts of particulates, such as typhoons or Asian dust storms, was also studied.     

The measurement of natural sulfur emissions from soils and vegetation: Three sites in the Eastern United States revisited

Sulfur fluxes from bare soils, naturally vegetated surfaces and from several agricultural crops were measured at two mid-continent sites (Ames, Iowa and Celeryville, Ohio) and from one salt water marsh site (Cedar Island, North Carolina) during a field program conducted jointly by the NOAA Aeronomy Laboratory, Washington State University Laboratory for Atmospheric Research and University of Idaho Department of Chemistry during July and August 1985. The sites were chosen specifically because they had been characterized by previous studies (Anejaet al., 1979; Adamset al., 1980, 1981). The NOAA gas chromatographic/dynamic-enclosure measurements yielded bare soil surfaces fluxes from the mid-continent sites composed predominantly of COS, H₂S, CH₃–S–CH₃ (DMS) and CS₂, all of which were strongly correlated with air temperature. Net fluxes of approximately 5 and 15 ng S/m² min were observed in Iowa and Ohio, respectively, at appropriate weighted mean July temperatures. These fluxes are roughly a factor of 10 smaller than the earlier measurements, the greatest difference being in the measurement of the H₂S flux. The presence of growing vegetation was observed to measurably increase the flux of H₂S, significantly increase that of DMS and to decrease that of COS. Sulfur fluxes in the Cedar Island environs were observed to be both spatially and temporally much more variable and to include CH₃SH as a measurable contributor. Net fluxes, composed predominantly of DMS and H₂S, were estimated to be about 300 ngS/m²min during August; again about a factor of 10 lower than previous estimates. All measurements were corroborated to within about a factor of 2 by those of the other participating laboratories.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

Wet removal of highly soluble gases

Partition, not kinetics, ultimately determines the concentration of highly soluble gases in cloud droplets. Partition equations are formulated and applied to idealized air-mass thunderclouds and precipitating stratus. Contribution to aqueous concentrations from sub-cloud scavenging of highly soluble gases is estimated at between 10 and 20% under relatively unpolluted conditions. Data indicate that evaporation can produce enhancements in concentration of as much as a factor of 3. The calculations give large-scale mean coefficients of wet removal of highly soluble gases of about 2.8×10^-6 s^-1 (4-day residence time) for air-mass thunderclouds and precipitating stratus. Removal is so effective that the mean scale heights of these gases should be decreased to 2 km or less. The criterion of high solubility in this paper is that K ^H (Henry's Law coefficient) > 10⁵ mol l^-1 atm^-1. Gases that are effectively highly soluble include HCl, HNO₃, H₂SO₄, H₂O₂, NH₃ in acid droplets, SO₂ in oxidizing droplets (and probably some light amines and sulfonic acids), but not SO₂ in the absence of oxidants, nor HCHO. A variation of removal coefficient and scale height with solubility is presented. A comparison of atmospheric NH₃ concentrations deduced from rain NH₄ ⁺ and measured directly gives reasonable agreement.     

On the scavenging of SO2 by cloud and raindrops: II. An experimental study of SO2 absorption and desorption for water drops in air

For the purpose of testing our previously described theory of SO₂ scavenging a laboratory investigation was carried out in the UCLA 33 m long rainshaft. Drops with radii between 250 and 2500 m were allowed to come to terminal velocity, after which they passed through a chamber of variable length filled with various SO₂ concentrations in air. After falling through a gas separating chamber consisting of a fluorocarbon gas the drops were collected and analyzed for their total S content in order to determine the rate of SO ₂ absorption.The SO₂ concentration in air studied ranged between 1 and 60% (v). Such relatively large concentrations were necessary due to the short times the drops were exposed to SO₂ in the present setup. The present experimental results were therefore not used to simulate atmospheric conditions but rather to test our previously derived theory which is applicable to any laboratory or atmospheric condition. Comparison of our studies with the results from our theory applied to our laboratory conditions led to predicted values for the S concentration in the drops which agreed well with those observed if the drops had radii smaller than 500 m. In order to obtain agreement between predicted and observed S concentrations in larger drops, an empirically derived eddy diffusivity for SO₂ in water had to be included in the theory to take into account the effect of turbulent mixing inside such large drops.In a subsequent set of experiments, drops initially saturated with S (IV) were allowed to fall through S-free air to determine the rate of SO ₂ desorption. The results of these studies also agreed well with the results of our theoretical model, thus justifying the reversibility assumption made in our theoretical models.In a final set of experiments, the effects of oxidation on SO₂ absorption was studied by means of drops containing various amounts of H₂O₂. For comparable exposure times to SO₂, the S concentration in drops with H₂O₂ was found to be up to 10 times higher than the concentration in drops in which no oxidation occurred.     

Trace gases and PM2.5-bound metal abundance over a tropical urban environment,South India

Pre and Post-Monsoon levels of ambient SO₂, NO₂, PM_2.5 and the trace metals Fe, Cu, etc. were measured at industrial and residential regions of the Kochi urban area in South India for a period of two years. The mean PM_2.5, SO₂ and NO₂ concentrations across all sites were 38.98?±?1.38 µg/m³, 2.78?±?0.85 µg/m³ and 11.90?±?4.68 µg/m³ respectively, which is lower than many other Indian cities. There was little difference in any on the measured species between the seasons. A few sites exceeded the NAAQS (define acronym and state standard) and most of the sites exceeded WHO (define acronym and state standard) standard for PM_2.5. The average trace metal concentrations (ng/m³) were found to be Fe (32.58)?>?Zn (31.93)?>?Ni (10.13)?>?Cr (5.48)?>?Pb (5.37)?>?Cu (3.24). The maximum concentration of trace metals except Pb were reported in industrial areas. The enrichment factor, of metals relative to crustal material, indicated anthropogenic dominance over natural sources for the trace metal concentration in Kochi’s atmosphere. This work demonstrates the importance of air quality monitoring in this area.

     

Chemical ionisation mass spectrometer for measurements of OH and Peroxy radical concentrations in moderately polluted atmospheres

A new version of an atmospheric pressure chemical ionisation mass spectrometer has been developed for ground based in situ atmospheric measurements of OH and total peroxy (HO₂ + organic peroxy) radicals. Based on the previously developed principle of chemical conversion of OH radicals to H₂SO₄ in reaction with SO₂ and detection of H₂SO₄ using an ion molecule reaction with NO₃^─, the new instrument is equipped with a turbulent chemical conversion reactor allowing for measurements in moderately polluted atmosphere at NO concentrations up to several ppb. Unlike other similar devices, where the primary NO₃^─ ions are produced using radioactive ion sources, the new instrument is equipped with a specially developed corona discharge ion source. According to laboratory measurements, the overall accuracy and detection limits are estimated to be, respectively, 25% and 2 × 10⁵ molecule cm^-3 for OH and 30% and 1 × 10⁵ molecule cm^-3 for HO₂ at 10 min integration times. The detection limit for measurements of OH radicals under polluted conditions is 5 × 10⁵ molecules cm^-3 at 10 min integration times. Examples of ambient air measurements during a field campaign near Paris in July 2007 are presented demonstrating the capability of the new instrument, although with reduced performance due to the employment of non isotopic SO₂.     

临安冬夏季SO2、NO2和O3体积分数特征及与气象条件的关系

对临安大气本底站2003-2004年冬、夏季二氧化氮(NO2)、二氧化硫(SO2)、臭氧(O3)进行了分析.结果表明:冬季NO2和SO2平均体积分数分别为19.48×10-9和35.74 x10-9,而夏季的平均体积分数分别为4.81×10-9和8.12×10-9,冬季高于夏季;O3在夏季的平均体积分数为33.55×10-9,略高于冬季的25.44×10-9;夜间NO2和SO2体积分数比白天高,并且NO2呈明显的单峰单谷型分布,O3也呈单峰型但峰值出现在白天.NO2、SO2体积分数存在着明显的“假日效应”,假日比非假日低,周五高于假日和非假日;但O3体积分数没有明显的假日效应.降水对SO2有明显的清除作用,但对NO2的清除作用不明显.与风向对比发现,夏季高体积分数的NO2、SO2都受到NW、WNW风的影响,冬季则分别受NE和SW、SSW风的影响;而O3受风向的影响较复杂,与局地光化学反应有关.