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1.
The goal of this study is to determine the chemical composition of rain, in the wider region of Athens, Greece for the time period 1st September 2001 to 31st August 2002. Two model automatic rain samplers were installed in the Meteorological Station of Laboratory of Climatology (latitude: 37° 58′ N, longitude: 23° 47′ E) inside the Athens University Campus and in a site at Heraklio Attica, a northern suburb of Athens (latitude: 38° 03′ N, longitude: 23° 45′ E). The concentrations (μeq l−1) of the major cations (H+, Na+, K+, Ca2+ and Mg2+) and anions (Cl−, , και ), as well as pH and conductivity of rain in 39 total samples were determined. The figures of pH range from 6.4 to 8.4 and conductivity from 8 to 207 μS cm−1. The analysis showed that Ca2+ ions are abundant within all examined samples, while and present the highest concentrations from the anions. In order to find out the origin of the air masses, the air mass back trajectories were calculated. Five sectors of the origin of air masses were revealed: the North, the South, the Local, the West and the East sector. Multivariate methods included Factor Analysis and Discriminant Analysis were applied to the examined ion concentrations and three main factors were extracted, which discriminated the ions according to their origin. The first group of ions is interpreted as the result of the anthropogenic activity, the second group represents the acidity–alkalinity independently of their source and the third one the marine influence.  相似文献   

2.
The present study investigated the chemical composition of wet atmospheric precipitation in India’s richest coal mining belt. Total 418 samples were collected on event basis at six sites from July to October in 2003 and May to October in 2004 and analysed for pH, EC, F−, Cl−, , , Ca2+, Mg2+, Na+, K+ and . The average pH value (5.7) of the rainwater of the investigated area is alkaline in nature. However, the temporal pH variation showed the alkaline nature during the early phase of monsoonal rainfall but it trends towards acidic during the late and high rainfall periods. The rainwater chemistry of the region showed high contribution of Ca2+ (47%) and (21%) in cations and (55%) and Cl− (23%) in anionic abundance. The high non seas salt fraction (nss) of Ca2+ (99%) and Mg2+ (96%) suggests crustal source of the ions, while the high nss (96%) and high ratio signifying the impact of anthropogenic sources and the source of the acidity. The ratio of varies from 0.03 to 3.23 with the average value of 0.84 suggesting that Ca2+ and play a major role in neutralization processes. The assessment of the wet ionic deposition rates shows no any specific trend, however Ca2+ deposition rate was highest followed by and .  相似文献   

3.
The two-year (1999–2000) rainwater chemistry at two monitoring sites in nearby coastal areas [Taiwan (TW) and Hong Kong (HK)] within the Western Pacific region has been studied. The volume weighted average pH values for the entire sampling period in TW and HK were 4.6 and 4.2, respectively. Sea salt Na+ and Cl− were the most abundant species in the TW samples but and H+ were the most abundant in the HK samples. The sea salt and concentrations at TW were higher than those at HK both in the cold and warm seasons. Chloride depletion was minimal in the rainwater samples at both sites. Non seasalt- was associated with . Under the influence of the East Asian Winter Monsoon, the back-trajectory studies revealed that elevated anthropogenic species concentrations were associated with trajectories (1) very near to the continental boundary layer of Mainland China; or (2) along the coastline of Eastern China where large cities/industrial areas are located or (3) passing through the region of stagnant air over Northern/Eastern China. The lowest anthropogenic and crustal species concentrations measured in HK are associated with the summer monsoon and are attributed not only to the clean marine air masses but also to the relatively low SO2, NO x and NH3 emissions from the South/ South East Asian countries, as well as infrequent biomass burning activities and wet scavenging at sources during the summer months. Approaching tropical cyclones led to the lowest pH values (4.2 in TW and 3.8 in HK) amongst the other weather categories. The findings here have been compared with other studies within East Asia and elsewhere.  相似文献   

4.
Levels of fine Particulate Matter (PMfine), SO2 and NOx are interlinked through atmospheric reactions to a large extent. NOx, NH3, SO2, temperature and humidity are the important atmospheric constituents/conditions governing formation of fine particulate sulfates and nitrates. To understand the formation of inorganic secondary particles (nitrates and sulfates) in the atmosphere, a study was undertaken in Kanpur, India. Specifically, the study was designed to measure the atmospheric levels of covering winter and summer seasons and day and night samplings to capture the diurnal variations. Results showed are found to be significantly high in winter season compared to the summer season. In winter, the molar ratio of to was found to be greater than 2:1. This higher molar ratio suggests that in addition to (NH4)2SO4, NH4NO3 will be formed because of excess quantity of present. In summer, the molar ratio was less than 2:1 indicating deficit of to produce NH4NO3. The nitrogen conversion ratio (NO2 to NO3) was found to be nearly 50% in the study area that suggested quick conversion of NO2 into nitric acid. As an overall conclusion, this study finds that NH3 plays a vital role in the formation of fine inorganic secondary particles particularly so in winter months and there is a need to identify and assess sources of ammonia emissions in India.  相似文献   

5.
The reactions of three structurally similar unsaturated alcohols, 2-buten-1-ol (crotyl alcohol), 2-methyl-2-propen-1-ol (MPO221) and 3-methyl-2-buten-1-ol (MBO321) with Cl atoms, have been investigated for the first time, using a 400 l Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID). The experiments were performed at atmospheric pressure and at temperatures between 255 and 298 K, in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions , , (in units of cm3 molecule−1 s−1). Finally, atmospheric lifetimes of those unsaturated alcohols with respect to OH, NO3, O3 and Cl have been calculated.  相似文献   

6.
The aqueous phase acid-catalyzed reaction of methanol (CH3OH) with nitric acid (HNO3) to yield methyl nitrate (CH3ONO2) under atmospheric conditions has been investigated using gas-phase infrared spectroscopy. Reactions were conducted in aqueous sulfuric acid solutions (50.5–63.6 wt.%) with [CH3OH] = 0.00005–0.005 M and [HNO3] = 0.02–0.21 M, at 278.2–328.6 K. Methyl nitrate production rates increased linearly with CH3OH and HNO3 concentrations and exponentially with sulfuric acid weight percent within the regime studied. Rates increased linearly with nitronium ion concentration, indicating that the reaction involves as the nitrating agent under these conditions. At 298 K, the rate of methyl nitrate production can be calculated from k obs [CH3OH][HNO3], where k obs  = 2.337 × 10−13(exp(0.3198*wt.% H2SO4)) when the solubility of CH3ONO2 in acidic solution is approximated by H* for pure water. The temperature dependence of the rate coefficient is related to solution composition, with activation energies of 59 and 49 kJ/mol at 51.1 and 63.6 wt.% H2SO4, respectively, when k is calculated from rate. The temperature dependence has also been parameterized for application to the atmosphere, but the small quantities of present in aerosol particles will result in methyl nitrate production rates too small to be of significance under most atmospheric conditions. An erratum to this article can be found at  相似文献   

7.
To investigate the atmospheric deposition of nutrients into the coastal and shelf regions of the northwest Pacific Ocean, observation sites were established upon Qianliyan Island (within the Yellow Sea) and the Shengsi Archipelago (within the East China Sea), respectively. Nutrient concentrations, including , were determined in both aerosols and rainwater samples. The analytical results contain clear seasonal signatures, with high values during the dry season and low values during the rainy season. Similar trends are observed for deposition fluxes. The amount of wet deposition is greater than that of dry deposition for the studied nutrient species. The influence of meteorological factors such as rainfall means that samples from Qianliyan Island record higher nutrient values than those from Shengsi. Along with riverine inputs, atmospheric deposition plays an important role in determining the biogeochemistry of nutrient species in coastal and shelf oceans. An erratum to this article can be found at  相似文献   

8.
This article presents a complete study of the diurnal chemical reactivity of the biogenic volatile organic compound (BVOC), 2-methyl-3-buten-2-ol (MBO) in the troposphere. Reactions of MBO with OH and with ozone were studied to analyse the respective parts of both processes in the global budget of MBO atmospheric reactivity. They were investigated under controlled conditions for pressure (atmospheric pressure) and temperature (298 ± 2 K) using three complementary European simulation chambers. Reaction with OH radicals was studied in the presence of and in the absence of NO x . The kinetic study was carried out by relative rate study using isoprene as a reference. The rate constant found for this reaction was molecule−1 cm3 s−1. FTIR spectroscopy, DNPH- and PFBHA-derivatisation analyses were performed for reactions with both OH radicals and ozone. In both reactions, the hydroxycarbonyl compound, 2-hydroxy-2-methylpropanal (HMPr) was positively identified and quantified, with a yield of in the reaction with OH, and a yield of and 0.84 ± 0.08 in the reaction with ozone under dry (HR < 1%) and humid conditions (HR = 20%–30%). A primary production of two other carbonyl compounds, acetone , and formaldehyde was found in the case of the dry ozonolysis experiments. Under humid conditions, only formaldehyde was co-produced with HMPr as a primary carbonyl compound, with a yield of . For the reaction with OH, three other carbonyl compounds were detected, acetone , formaldehyde and glycolaldehyde . In addition some realistic photo-oxidation experiments were performed to understand in an overall way the transformations of MBO in the atmosphere. The realistic photo-oxidation experiments were conducted in the EUPHORE outdoor simulation chamber. It was found that this compound is a weak secondary aerosol producer (less than 1% of the carbon balance). But it was confirmed that it is a potentially significant source of acetone, Δ[Acetone]/Δ[MBO] = 0.45. With our experimental conditions ([MBO]0 = 200 ppb, [NO]o = 50 ppb), an ozone yield of Δ[O3]/Δ[MBO] = 1.05 was found.  相似文献   

9.
This is the first study, which shows both NH3 and NH4+ to inhibit the autoxidation of aqueous SO2 in the pH range 7.0–8.5. The rate of the autoxidation, R aut , in both buffered and unbuffered media at a fixed pH is in conformity with the rate law:
where R 0 is rate in the absence of the inhibitors, B is a pH dependent empirical constant and [Inh]T is the analytical concentration of NH3 or NH4+. Both ammonia and ammonium ions appear to inhibit the autoxidation either by scavenging SO4− radicals or by forming less-reactive /unreactive Co(II)-NH3 complexes or both. The atmospheric relevance of the inhibition by ammonia and ammonium ions is discussed.  相似文献   

10.
Ambient suspended particles (TSP) were collected from January to June 2001 at seven sampling sites in western Macedonia, Greece, where four thermal power stations are located. TSP samples were chemically characterized for minerals (Fe, Al, Mg, Ca, K, Ti and Si), trace elements (P, Cd, Cr, Cu, Mn, Pb, V, Zn, Te, Co, Ni, Se, Sr, As, and Sb), water-soluble ions , carbonaceous compounds (OC/EC) and polycyclic aromatic hydrocarbons (PAHs). These classes of compounds were consequently compared with PM mass concentrations of TSP in order to perform mass closure. PM chemical compositions exhibited differences at the seven sites. Minerals were found to be more abundant at four sites, electrolytes dominated the composition at two of the sites while carbonaceous material was most abundant only at one site. The fraction unaccounted for ranged between 22 and 34%. Spatial variations of atmospheric concentrations showed significantly higher levels of minerals, some trace metals and TC at the site that was closest to the power plants. At the same site ions exhibited high correlations with minerals and the majority of trace elements.  相似文献   

11.
We present surface-layer measurements of temperature fluctuation variance from a site characterized by small-scale inhomogeneities. Periods of marked radiative forcing are selected. The data characterized by diabatic conditions and vertical heat flux larger than some threshold (here, chosen to be 0.01 K ms−1) agree quite well with the convective scaling in unstable cases, and with the z-less parameterisation (with a large scatter) in stable cases. For near-neutral cases, the similarity function diverges because of the loss of significance of the temperature scale. Departures from similarity are highlighted in cases with smaller thermal fluxes, because horizontal heterogeneity and unsteadiness become important as production terms.  相似文献   

12.
Simulations of oxidized nitrogen performed withglobal transport tracer models systematicallyunderestimate the concentrations of total nitrate atremote marine locations in the Mid-Pacific. Higheremission rates in the models of nitrogen oxides( ) from continental sources or alarger influx from the stratosphere do not seem tobe able to account for the shortfall. We are led toconclude that there has to be a substantial sourcelocated in oceanic areas. We speculate that -emission from electrical discharges overthe oceans could be the source we are looking for.Airborne observations of atmospheric concentrationsof oxidized nitrogen and ozone in the remoteatmosphere and observations of nitrate wetdeposition in remote sites are used as additionalconstraints to check the plausibility of thishypothesis. We find that a larger emission of due to lightning activity over the oceansindeed results in a much improved simulation oftotal nitrate in the remote Pacific, particularly inthe Equatorial and Tropical South Pacific and thatsuch a scenario is generally consistent withavailable observations of nitrate wet deposition andatmospheric concentrations of oxidized nitrogen andozone. An alternative hypothesis is that there is ahitherto unknown in situ source of over thePacific Ocean.  相似文献   

13.
The reaction kinetics of S(IV) autoxidation catalyzed by Mn(II) in the pH range 3–5 typical for atmospheric liquid water, was investigated. For reactions with pH maintained constant during the reaction course, the predictions obtained by a simple integral approach cover kinetic results only for concentrations of HSO 3 − up to 0.2 mM at pH 4.5. Thus, a generalized simple kinetic model, which can be used for predicting the reaction kinetics in wider concentration, pH and temperature ranges, was derived. This model is based on the assumption that the reaction rate is proportional to the concentration of a transient manganese-sulfito complex formed in the initial step of a radical chain mechanism. In the proposed power law rate equation
the concentration of complex is calculated from the stability constant K and concentrations of reactants at a specific reaction time. This rate equation adequately predicts the reaction kinetics in the pH range 3–5, in the concentration ranges 0.1 ≤ [HSO 3 − ] ≤ 0.4 mM and 2 ≤ [Mn(II)] ≤ 14.6 μM. For the temperature range 15–35 °C, the estimated value for activation energy is 92.0 ± 0.1 kJ mol−1 and the Gibbs free energy of formation of the manganese-sulfito complex is −20.4 ± 0.3 kJ mol−1. Furthermore, the kinetics for catalytic reactions with pH maintained constant during the reaction course as well as with initial pH adjusted only at the start of the reaction, is described satisfactorily by the present model.  相似文献   

14.
A tree-ring 14C record and a simple box model of the global 14C cycle are combined using a method of optimal estimation theory (Rauch-Tung-Striebel smoother). The combination is used to infer information about the time evolution of 14C production in the atmosphere for the period 9400 year BC to AD 1900 year. Unlike previous attempts to infer changes from the tree-ring record, the errors in both the 14C data and the model, which are assumed to be purely random (not systematic), are formally considered. The optimal time evolution of is compared to independent evidence of changes in cosmogenic nuclide production over the Holocene from a variety of records on their original chronology, e.g., a record of the virtual axial dipole moment (VADM) based on a compilation of archeomagnetic data, the record of 10Be concentration from the GISP2 ice core (Central Greenland), and the record of 10Be concentration from the PS1 ice core (South Pole). The rank correlations between and are highly significant (p < 0.01), indicating that geomagnetic field intensity and 10Be concentration in GISP2 and PS1 changed monotonically with 14C production. The linear correlation coefficients between are also highly significant (p<0.01) but relatively small (–0.76, 0.48, and 0.60, respectively). Thus, an important fraction (42–77%) of the variance in the geomagnetic and 10Be data is not accounted for by linear regression on the 14C productions implied by the tree-ring record. The variance near the 1500 yr period, which previous authors interpreted as solar variability, represents a small fraction of the total variance in the time series (<15% for the band 1200–1800 yr) and does not correspond to a spectral peak. Hence, the hypothesis of a direct solar forcing mechanism for the postulated millennial climate variability during the Holocene is not supported.  相似文献   

15.
Reactions of levoglucosan with produced from Fenton chemistry were studied in solution serving as a proxy for biomass burning aerosols. Two modes of oligomerization (≤2000 u) were observed for reaction times between 1 and 7 days using matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF-MS) and laser desorption ionization time-of-flight mass spectrometry (LDI-TOF-MS). Single-mass unit continuum mass distributions with dominant −2 u patterns were measured and superimposed by a +176/+162 u oligomer series. This latter oligomer pattern was attributed to a Criegee rearrangement (+14 u) of levoglucosan, initiated by , forming a lactone (176 u). The acid-catalyzed reaction of any ROH from levoglucosan (+162 u) forms an ester through transesterification of the lactone functionality, whereupon propagation forms polyesters. Proposed products and chemical mechanisms are suggested as sources and precursors of humic-like substances (HULIS), which are known to possess a large saccharic component and are possibly formed from biomass burning aerosols (Andreae, Global Biomass Burning, MIT Press, Cambridge, Massachusetts, 3–21, 1991).  相似文献   

16.
The applicability of the log-linear profile relationship over rough terrain to a height of 126 m is investigated. Simultaneous hourly averaged mean wind and temperature profiles measured at the Brookhaven meteorological tower during stable conditions are used in the analysis. The tower was surrounded by fairly homogeneous vegetation to a height of about 8 m. The results indicate that the log-linear profile relationship is valid at least for a height of 126 m for stabilities with Richardson numbers less than the critical value of 0.25. The mean value of in is found to be about 5.2 for these stabilities. The log-linear profile relation is found to be applicable for profiles observed beyond the critical stability; but the height of validity seems to decrease to about 100 m and the mean value of is about 1.6.Research performed under the auspices of the United States Energy Research and Development Administration (Contract E(30-1)-16).  相似文献   

17.
Alkyl nitrate yields from the NO x photooxidations of neopentane, 2-methylbutane and 3-methylpentane have been determined over the temperature and pressure ranges 281–323 K and 54–740 torr, respectively. The formation of the alkyl nitrates is attributed to the reaction pathway (1b) $${\text{RO}}_{\text{2}} + {\text{NO}}^{{\text{ }}\underrightarrow {\text{M}}} {\text{ RONO}}_{\text{2}}$$ and rate constant ratios k 1b/(k 1a+k 1b) are estimated, where (1a) is the reaction pathway (1a) $${\text{RO}}_{\text{2}} + {\text{NO}} \to {\text{RONO}}_{\text{2}} .$$ A method for estimating this rate constant ratio for primary, secondary and tertiary alkyl peroxy radicals is presented.  相似文献   

18.
A dataset from two campaigns conducted at the Vielsalm experimental site in Belgium was used as a basis for discussing some methodological problems and providing intermediate results on estimating CO2 advection. The analysis focused on the horizontal [CO2] gradient and on the vertical velocity w, the variables most affected by uncertainty. The sampling error for half-hourly horizontal [CO2] gradients was estimated to be 1.3 μmol mol−1. Despite this important random error for half-hour estimations of [CO2], the mean horizontal [CO2] gradients in advective conditions were shown to be representative at the ecosystem scale and to extend only to the lowest part of a drainage sub-layer, which developed in the trunk space. By contrast, under daytime conditions, this gradient was shown to be more sensitive to local source heterogeneities. The estimation of the short-term averaged vertical velocity ( was the greater source of error when computing advection terms. The traditional correction methods used to obtain are discussed and a (co)sine correction is tested to highlight the instrumental origin of the offset in w. A comparison of measurements by sonic anemometers placed close together above the canopy showed that the uncertainty on was 0.042 m s−1, which is of the same order of magnitude as the velocity itself. In addition, as the drainage sub-layer is limited to the lowest part of the canopy, the representativeness of is questionable. An alternative computation using the divergence of the horizontal wind speed in the trunk space produced a estimation that was four times lower than the single-point measurement. However, this value gives a more realistic estimate of the vertical advection term and improves the CO2 budget closure at the site.  相似文献   

19.
In steady, neutrally-stratified flow over uniform terrain, the Kolmogorov constant for the one-dimensional spectrum in the inertial subrange (α 1) and the von Karman constant of the logarithmic profile (k) are shown to be related by $$\alpha _1 k^{{4 \mathord{\left/ {\vphantom {4 3}} \right. \kern-\nulldelimiterspace} 3}} = \left[ {\frac{{\sum \phi }}{{0.555}}} \right]\left[ {\frac{{nz}}{{\bar U_z }}} \right]^{{2 \mathord{\left/ {\vphantom {2 3}} \right. \kern-\nulldelimiterspace} 3}} \left[ {\frac{{\ln z_2 /z_1 }}{{\bar U_2 - \bar U_1 }}} \right]^2 \simeq 0.136,$$ , where the numerical value results from field measurements recorded in near-ideal conditions. This experimentally-observed Kolmogorov-von Karman ‘K-von K’ product is close to the value designated by a one-dimensional equivalent of the theoretical relation previously given by Roth (1970). More-over, it is in remarkably close agreement with new values of both constants independently proposed in recent years.  相似文献   

20.
Near-surface wind profiles in the nocturnal boundary layer, depth h, above relatively flat, tree-covered terrain are described in the context of the analysis of Garratt (1980) for the unstable atmospheric boundary layer. The observations at two sites imply a surface-based transition layer, of depth z *, within which the observed non-dimensional profiles Φ M 0 are a modified form of the inertial sub-layer relation \(\Phi _M \left( {{z \mathord{\left/ {\vphantom {z L}} \right. \kern-0em} L}} \right) = \left( {{{1 + 5_Z } \mathord{\left/ {\vphantom {{1 + 5_Z } L}} \right. \kern-0em} L}} \right)\) according to $$\Phi _M^{\text{0}} \simeq \left( {{{1 + 5z} \mathord{\left/ {\vphantom {{1 + 5z} L}} \right. \kern-\nulldelimiterspace} L}} \right)\exp \left[ { - 0.7\left( {{{1 - z} \mathord{\left/ {\vphantom {{1 - z} z}} \right. \kern-\nulldelimiterspace} z}_ * } \right)} \right]$$ , where z is height above the zero-plane displacement and L is the Monin-Obukhov length. At both sites the depth z * is significantly smaller than the appropriate neutral value (z *N ) found from the previous analysis, as might be expected in the presence of a buoyant sink for turbulent kinetic energy.  相似文献   

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