A comparison of several diffuse solar radiation models for Greece

Summary This paper attempts to test the applicability of existing correlation models to the estimation of diffuse radiation with respect to measured values at a station. There are two types of model: The first type depends on the fraction of monthly average daily diffuse radiation to total solar radiation, , as a function of the clearness index, . The second type expresses the fraction or as a function of the sunshine fraction Therefore, it presents statistically based correlations between global radiation and its diffuse component on a horizontal surface and suggests two equations to determine the ratio of diffuse radiation to total radiation received on a horizontal surface. The results of these correlation equations are compared with other accepted equations.With 3 Figures     

Transformation of Irradiance Measurements into Spectral Actinic Flux for Photolysis Rates Determination

The actinic flux is the only radiometric quantity suitable for photolysisfrequency determination. It is derived from solar spectral irradiancemeasurements performed by a portable spectroradiometer in the 300–850nm wavelength range. The spectral irradiance is first divided into a directpart and a diffuse part, according to the atmospheric conditions, and thenconverted into the corresponding actinic flux quantity. As an intermediary,the ratio of diffuse actinic flux to diffuseirradiance is calculated by the spherical harmonics radiative code withrespect to wavelength, solar zenith angle, surface albedo, and aerosolproperties.The results of extensive sensitivity studies of asa function of the main atmospheric parameters are discussed and lead to theconclusion that aerosol optical depth is the major critical value for aprecise determination. The global algorithm totransform spectral irradiance into actinic flux is finally applied forphotodissociation rate calculations by convolution of the obtained actinicflux spectra with the absorption cross-sections and quantum yields of themolecule studied. Photolysis rates of different atmospheric photooxidants havebeen measured with this spectroradiometric method during the summers of 1993and 1994 in Brittany and in Portugal. The ozone and nitrogen dioxidephotodissociation rates obtained present a good agreement with thej(O₃) and j(NO₂) actinometerresults, for the same experimental conditions in Brittany.     

Role of atmospheric ammonia in the formation of inorganic secondary particulate matter: A study at Kanpur,India

Levels of fine Particulate Matter (PM_fine), SO₂ and NO_x are interlinked through atmospheric reactions to a large extent. NO_x, 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.     

Chemistry of Precipitation Events and Inter-Relationship with Ambient Aerosols over a Semi-Arid Region in Western India

The precipitation events (n = 91), collected for 3 years (2000–2002) during the period of SW-monsoon (Jun–Aug) from an urban site (Ahmedabad, 23.0°N, 72.6°E) of a semi-arid region in western India, are found to exhibit characteristic differences in terms of their solute contents. The low solute (<700 μeq L⁻¹) events are either marked by heavy precipitation amount or successive events collected during an extended rain spell; whereas light precipitation events occurring after antecedent dry period are characterized by high solutes (>700 μeq L⁻¹). The ionic composition of low solute events show large variability due to varying contribution of anthropogenic species (: 1%–74%; : 1%–25%; and : 8%–68%) to the respective ion balance. In high solute events, ionic abundances are dominated by mineral dust (Ca²⁺ and ) and sea-salts (Na⁺ and Cl⁻). These differences are also reflected in the pH of low solute events (range: 5.2–7.4, VWM: 6.4) and high solute events (range: 6.6–8.2, VWM: 7.3). The comparison of Ca²⁺/Na⁺ and nss- ratios (on equivalent basis) in rain and aerosols suggests that the ionic composition of high solute events is influenced by below-cloud scavenging; whereas evidence for in-cloud scavenging is significantly reflected in low solute events. The annual wet-deposition fluxes of and are 330 and 480 mg m⁻² y⁻¹, respectively, in contrast to their corresponding dry-deposition fluxes (14 and 160 mg m⁻² y⁻¹); whereas wet and dry removal of Ca²⁺, Mg²⁺ and are comparable.     

A multifractal analysis of lidar measured water vapour

Accurate and fast-response measurements of space-time observations of specific humidity were made above a drying land surface at the University of California at Davis, using the Los Alamos water Raman-lidar. In an attempt to quantify the space-time intermittency features of turbulent flows in the lower atmosphere, a multifractal analysis of these water vapour measurements was performed. The structure of the specific humidity, (x, t), was analyzed quantifying a scalar gradient measure both in time and space, for all possible one-dimensional cuts, i.e. and . The results confirm the multifractal nature of this scalar gradient measure (a type of scalar dissipation rate) and show that humidity measurements at fixed times (x) are more intermittent (e.g. have less entropy dimension) than those at fixed locations in space (t). Similar multifractal behaviour of the spatial data, with and without a transformation from the observed wind velocities, supports the validity of Taylor's hypothesis for the studied fields.     

Chemical characterization of wet precipitation events and deposition of pollutants in coal mining region,India

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 _.     

On the profiles of wind velocity in the roughness sublayer above a coniferous forest

Wind velocity and temperature measurements from a 200 m tower, locatedin a forest near Karlsruhe were used to investigatethe modified profile function of the wind velocity in theroughness sublayer.To avoid determination of the friction velocity we introduced analternative analysis with the expression instead of From the observed Fm* profiles we evaluated the profile function m*. The wind profiles observed under neutral conditions were well representedby a modified non-dimensional profile function with physically based boundary values at the top and at the bottom of theroughness sublayer.The results of our analysis can be used to take into consideration themomentum exchange between the atmosphere and a forest in mesoscaleatmospheric models in a refined way.     

The acid catalyzed nitration of methanol: formation of methyl nitrate via aerosol chemistry

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     

Chemical composition of wet deposition in a Mediterranean site Athens,Greece related to the origin of air masses

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.     

Formation of Organic Aerosols from the Oxidation of Biogenic Hydrocarbons

Measurements of aerosol formation during thephotooxidation of -pinene, -pinene,d-3-carene, d-limonene, ocimene, linalool, terpinene-4-ol, andtrans-caryophyllene were conducted in anoutdoor smog chamber. Daylight experiments in thepresence of and dark experiments withelevated ozone concentrations were performed. Theevolution of the aerosol was simulated by theapplication of a gas/particle absorption model inconnection with a chemical reaction mechanism. Thefractional aerosol yield is shown to be a function ofthe organic aerosol mass concentration andtemperature. Ozone and, for selected hydrocarbons, theNO₃ reaction of the compounds were found torepresent efficient routes to the formation ofcondensable products. For initial hydrocarbon mixingratios of about 100 ppb, the fractional aerosol yieldsfrom daylight runs have been estimated to be 5%for open-chain hydrocarbons, such as ocimene andlinalool, 5–25% for monounsaturated cyclicmonoterpenes, such as -pinene, d-3-carene, orterpinene-4-ol, and 40% for a cyclic monoterpenewith two double bonds like d-limonene. For the onlysesquiterpene investigated, trans-caryophyllene, afractional aerosol yield of close to 100% wasobserved. The majority of the compounds studied showedan even higher aerosol yield during dark experimentsin the presence of ozone.     

Characterization of nutrients in the atmospheric wet and dry deposition observed at the two monitoring sites over Yellow Sea and East China Sea

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     

A dual site study of the rainwater chemistry within the Western Pacific region

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.     

Mass closure of total suspended particles over the coal burning power production area of western Macedonia, Greece

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.     

Alkyl nitrate formation from the reaction of a series of branched RO2 radicals with NO as a function of temperature and pressure

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.     

Simulation Chamber Studies of the Atmospheric Oxidation of 2-Methyl-3-Buten-2-ol: Reaction with Hydroxyl Radicals and Ozone Under a Variety of Conditions

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.     

Effects of water vapour on the structure parameter of the refractive index for near-infrared radiation

The refractive index of air (n) mainly depends on temperature andwater vapour content. For near-infrared radiation, temperature isthe main determining factor. To determinethe structure parameter of temperature ( ) fromthe structure parameter of the refractive index( ), the influence ofwater vapour content on n needs to be taken into account as acorrection. Three levels of approximation are presented. The firstinvolves the standard deviations of T and q (_T and_q) as well as the correlation coefficient betweenT and q (R_Tq). The second approximation involvesR_Tq and the Bowen ratio (), and the last uses only the Bowen ratio.The latter is the classical Bowen ratio correction.Evaluation of the validity of the assumptions used in the derivationreveals that a large error may be introduced (for situations withR_Tq < 0.8) by replacing _T/_qwith the Bowen ratio.Consequently, estimating from using the Bowen ratiocan contain errors of 5–40% for || < 1. Adding R_Tqas extra information reduces the errors only marginally. For || > 1,the correction is small, and all three approximations give errors of lessthan 1% in . When is used to compute the sensible heat flux,the influence of the quality of the correction forwater vapour fluctuations on the measured energy balance is small: forsmall ||, the correction is large, but the absolute value ofthe heat flux is small, whereas for large ||, the correctionis insignificant.     

Validity of the log-linear profile relationship over a rough terrain during stable conditions

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).     

Interpolation between Businger–Dyer Formulae and Free Convection Forms: A Revised Approach

In this study, profile functions for flux calculations during unstable conditions are proposed and examined. These functions are based on a direct interpolation for the dimensionless wind speed and temperature gradients between the standard Businger–Dyer formulae, , , and free convection forms, , being the Monin–Obukhov stability parameter. A previously presented interpolation between the corresponding profile relationships, in attempting to provide a general relationship for the whole unstable regime, leads to serious restrictions for the values of in the free convection forms. These restrictions rendered available experimental data almost inapplicable, since the behaviour of the formulae in the near-neutral range controls the values of those parameters. The proposed interpolation provides functions that, firstly, fit the standard Businger–Dyer forms for near-neutral conditions and, secondly, satisfy the asymptotic behaviour as , permitting wider ranges of possible values. This step is very important, taking into account the large spread of the experimental data. Thus, as further and more accurate observations at strong instability become available, this approach could prove very efficient in fitting these data while retaining correct near-neutral behaviour.     

Kinetics of the reactions of Cl atoms with 2-buten-1-ol, 2-methyl-2-propen-1-ol, and 3-methyl-2-buten-1-ol as a function of temperature

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.     

The influence of stratification on heat and momentum turbulent transfer in antarctica

Data from the Antarctic winter at Halley Base have been used in order to evaluate qualitatively and quantitatively how the stratification in the low atmosphere (evaluated with the gradient Richardson number, Ri) influences the eddy transfers of heat and momentum. Vertical profiles of wind and temperature up to 32 m, and turbulent fluxes ( , and ) measured from three ultrasonic thermo-anemometers installed at 5, 17 and 32 m are employed to calculate Ri, the friction velocity (u _*) and the eddy diffusivities for heat (K _h ) and momentum (K _m ). The results show a big dependence of stability onK _m ,K _h andu _*, with a sharp decrease of these turbulent parameters with increasing stability. The ratio of eddy diffusivities (K _h /K _m ) is also analyzed and presents a decreasing tendency as Ri increases, reaching values even less than 1, i.e., there were situations where the turbulent transfer of momentum was greater than that of heat. Possible mechanisms of turbulent mixing are discussed.