Distribution of some ions and minor gaseous components by concentrations in the atmospheric surface layer of some regions in Eastern Siberia and the Far East

We consider the resemblance between the ion composition of the fraction of soluble aerosols and gaseous admixtures in the atmospheric surface layer at the high-level Mondy station (East Sayan), those in the Listvyanka settlement south of Lake Baikal, in the city of Irkutsk, and at the Primorskaya station near the city of Ussuriysk (Primorskii krai). We use measurement data on the concentrations of the following ions: HCO ₃ ^? , SO ₄ ^2? , NO ₃ ^? , Cl^?, H⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺ in the soluble fraction of aerosols and gases HNO₃, HCl, NH₃, and SO₂ in air samples over a 10-year period conducted in the mode of online monitoring. We found the lognormal form of distributions of concentrations of each of the abovementioned components according to the number of samples. A versatile scheme of the distribution of mean geometric concentrations of atmospheric components was proposed for all four groups.     

On the Nature of Aerosol Particles in the Atmosphere of Irkutsk

Monitoring data on the ion composition of precipitation and the water-soluble fraction of aerosol have been used to identify two types of aerosol particles in the surface atmosphere of Irkutsk (“metal” and “ammonia” groups). The aerosol acidity is basically governed by the acidity of ammonia particles, and the ion composition depends on air relative humidity (RH). Preliminary estimates are given for the distribution of major cations and anions by aerosol groups.     

渤海湾北部和西部海域表层沉积物中无机碳形态研究

采用氯化钠(NaC1)、氨水(NH3·H2O)、氢氧化钠(NaOH)、盐酸羟胺(NH2OH·HC1)溶液对渤海湾北部和西部海域表层沉积物中无机碳进行了连续浸取,并将无机碳分为5种赋存形态:交换态(NaCl相)、弱碱结合态(NH3·H2O相)、强碱结合态(NaOH相)、弱酸结合态(NH2OH·HCl相)和残渣态.同时,结...     

Carbonaceous aerosols of aviation and shipping emissions

This is a study of the physical and chemical properties of carbonaceous aerosols emitted by transport systems (namely, by aircraft gas turbine engines and large ship diesel engines) into the atmosphere. A comparative analysis of the morphology, size, elemental composition, and surface chemistry between aviation and diesel soot particles reveals the general and characteristic features of emissions from each source. The high pollution rate of diesel soot particles, considerable fraction of metal admixtures, and availability of char particles characterize the specific features of the formation of particles of this type. The main characteristics characterizing the interaction between aviation and shipping emission aerosols in the moist atmosphere (the composition of organic and water-soluble fractions at the surface) have been obtained. Due to high hygroscopicity, the microparticles can generate cloud condensation nuclei and initiate contrails and additional tropospheric cloudiness.     

Trends in the solubility of iron,aluminium, manganese and phosphorus in aerosol collected over the Atlantic Ocean

The solubility of iron, aluminium, manganese and phosphorus has been determined in aerosol samples collected between 49°N and 52°S during three cruises conducted in the Atlantic Ocean as part of the European Union funded IRONAGES programme. Solubilities (defined at pH 4.7) determined for Fe and Al in samples of Saharan dust were significantly lower (medians 1.7% and 3.0%, respectively) than the solubilities of these metals in aerosols from other source regions (whole dataset medians 5.2% and 9.0%, respectively). Mn solubility also varied with aerosol source, but the median solubility of Mn in Saharan dust was very similar to the median for the dataset as a whole (55% and 56%, respectively). The observed solubility of aerosol P was ∼ 32%, with P solubility in Saharan aerosol perhaps as low as 10%. Laboratory studies have indicated that aerosol Fe solubility is enhanced by acid processing. No relationship could be found between Fe solubility and the concentrations of acid species (non-seasalt SO₄²⁻, NO₃⁻) nor the net acidity of the aerosol, so we are unable to confirm that this process is significant in the atmosphere. In terms of the supply of soluble Fe to oceanic ecosystems on a global scale, the observed higher solubility for Fe in non-Saharan aerosols is probably not significant because the Sahara is easily the dominant source of Fe to the Atlantic. On a smaller scale however, higher solubility for aerosol Fe may alter our understanding of Fe cycling in regions such as the remote Southern Ocean.     

Influence of chemical composition and microstructure on the hygroscopic growth of pyrogenic aerosol

The hygroscopic properties of a model smoke aerosol series including ammonium sulfate, levoglucosan, and oxalic and humic acids were investigated. The condensation growth of particles and the relative humidity of direct and inverse particle-droplet phase transitions were measured with a tandem differential mobility analyzer. The data were obtained in the range of relative humidity from 4 to 95% at 298 K. Experimental growth factors were compared to the results of Koehler theory by using contemporary models of water activity in particles. It was shown that the hygroscopic properties of the aerosols were substantially different from the hygroscopic properties of the corresponding bulk phases. It was found that a complex microstructure of nanoparticles resulted in excess volume absorption of water, in some cases causing their full deliquescence at lower relative humidities than in macrosystems of identical composition. From the measurement data, a parametrization of hygroscopic particle growth was performed. The results of parametrization can be used to construct refined models of a smoke aerosol.     

Chemical Composition of North Atlantic Aerosols

The paper presents new information on the chemical composition of the insoluble aerosol fraction in the atmospheric surface boundary layer of different climatic zones of the North Atlantic (temperate humid, arid and semiarid, equatorial humid). The material for this study was collected during 12 expeditions. Nylon meshes were used to catch aerosols along the course of vessels. Aerosols above the North Atlantic consist of lithogenic, biogenic, and anthropogenic particles transported from different regions, which governs the differences in their concentrations and mineral and chemical compositions. Significant (by more than an order of magnitude) enrichment of aerosols in Cu, Cd, Zn, Pb, Sb, and Se is related to anthropogenic atmospheric pollution.     

黄河三角洲浅层地下水化学特征与演化

2009年4月~2010年3月连续2年对黄河三角洲19口地下水监测井进行观测并对地下水离子化学成分分析,探讨了该区域浅层地下水化学成分、水化学类型及演化规律,为揭示区域地下水环境特征和演化具有现实意义。结果表明,黄河三角洲地区地下水p H值变化较小,地下水埋深较浅且年内变化幅度为1.0~3.0 m,但矿化度和各离子差异明显,地下水以Na+、Cl–占绝对优势;矿化度较低的测井的离子浓度变幅较小,反之,矿化度高的测井离子浓度变幅较大;地下水化学类型分为氯化物型、重碳酸盐氯化物型、重碳酸盐氯化物硫酸盐型和硫酸盐重碳酸盐型四大类型,主要包括Na+-Cl–、Na+-Cl–.3HCO?、Na+-Cl–.3HCO?、Na+-Cl–.3HCO?.24SO?、Na+-3HCO?.Cl–.24SO?和Na+-24SO?.3HCO?六种子类型,氯化物型主要分布于广饶县咸水入侵区和滨海区域,重碳酸盐氯化物型主要分布于黄河三角洲保护区内,重碳酸盐氯化物硫酸盐型分布在广饶县咸水入侵区,硫酸盐重碳酸盐型主要分布在靠近黄河流路附近;根据黄河三角洲流路变迁和Gibbs模型,黄河三角洲地区水样化学组成均落在Gibbs提出的Boomerang Envelope模型右上翼,表明研究区水样化学组成主要受蒸发和沉淀作用,海水控制起次要作用,土地利用变化、灌溉、施肥等人为活动的影响亦不能忽视。     

硫酸铵对条斑紫菜生长和单孢子形成、放散与附着的影响

作者研究了(NH_4)_2SO_4的浓度对条斑紫菜生长和单孢子形成、放散与附着的影响。在室内培养条件下,条斑紫菜的生长和单孢子形成、放散、附着要求的营养条件不完全一致。当硫酸铵的浓度增加到一定量时紫菜的生长受到抑制;低浓度时,单孢子的放散、附着少;高浓度时,单孢子放散、附着的多。     

Sulphate complexation in seawater: A relation between the stability constants of sodium sulphate and magnesium sulphate in seawater from a determination of the stability constant of hydrogen sulphate and a calculation of the single ion activity coefficient of sulphate

The conditional stability constant of HSO₄^? has been determined at 25°C, 1 atm and a formal ionic strength of 0.7 M in solutions containing sodium, magnesium, chloride and sulphate. This was done spectrophotometrically (UV), using diphenylamine as indicator. The value obtained was 17.0 ± 0.1 (molar scale). Single ion activity coefficients for Na₂SO₄, K₂SO₄ and MgSO₄ have been calculated according to the Bates et al. (1970) model, assuming that the sulphate ion is not hydrated. It was found that the single ion activity coefficient of sulphate changes very little between Na₂SO₄, K₂SO₄ and MgSO₄ when the formal ionic strength is kept constant.These results have been used to obtain relations between the stability constants of NaSO₄^? and MgSO₄ valid for seawater.     

Electrization of aerosol wetted in bipolarly ionized air

We studied the influence of the characteristics of the atmospheric ionization and physical-chemical state of condensation nuclei on the electric state of convective cells. Based on the results of experiments in an adiabatic chamber with a volume of 3200 m³, we found that, with increase in relative air humidity H from 40 to 95% with an equivalent ascent rate of 100–400 cm/s, excessive charges in amounts of about 10³ or more elementary charges per cm3 may be accumulated on the nuclei. The sign of the charge depends on the chemical composition of the hygroscopic nuclei. For instance, media with insoluble nuclei (porous silica, etc.) typically have prevailing negative charges; those with soluble nuclei (sodium chloride, etc.) are dominated by positive charges. At H = 60−90%, the electrization of soluble nuclei can be interpreted in the diffusion-kinetic models of the ion charging of aerosols. Considerable negative volume charges, which appear on insoluble hygroscopic nuclei during a rise in humidity from 40 to 70%, are explained by the structuring of surface water films, which exhibit a resemblance to negative lightweight ions. At high values (H > 90%), it is necessary to take into account the resemblance of the wetted surfaces to positive lightweight ions. We showed for the first time that, at ion formation rates of 3 and 1010 ion pairs/(cm³ s), the differences in the volume charge and wetting rate of condensation nuclei are insignificant. It is concluded that, in many meteorological situations, the first stage of electrization of the convection-derived cloud media is the ion charging of the condensation nuclei.     

Temporal variability of the chemical composition of surface aerosol in the Moscow region in 1999–2005 from the results of infrared spectroscopy of aerosol samples

The temporal variability of the chemical composition of surface aerosol with particle diameters of 0.7–2 μm is analyzed. This analysis is based on the results of measurements of infrared transmission spectra of aerosol samples collected with the use of a cascade impactor at the Zvenigorod Scientific Station of the Institute of Atmospheric Physics (IAP) in 1999–2005. Seasonal features of the aerosol chemical composition and its dependence on the particle size are revealed. The interdiurnal variability of the aerosol composition depends on the season, and it manifests itself more strongly in winter and spring. Air-mass changes lead to changes in the relation of sulfates and nitrates in the micron fraction of aerosol. The enrichment of samples in nitrates is especially characteristic of the winter and spring seasons. Compounds containing the NO₂ group are often met in the samples of aerosol with particle sizes of 0.7–1.3 μm during the cold time of the year. The estimates of the optical thickness of micron aerosol in the sulfate absorption band are obtained, and optical-thickness variations of some scales are detected. The quantitative characteristics of statistical relations between different chemical components of aerosol inside individual fractions and between chemical components of the micron and submicron fractions are obtained and analyzed.     

预处理方法对海洋微藻Isochrysis zhanjiangenisis脂肪酸组成及稳定碳同位素的影响

This study aims to quantify the effects of different pretreatment methods on the stable carbon isotope values of fatty acids in marine microalgae(Isochrysis zhanjiangenisis).To identify the effects of sample preparation on theδ~(13)C value and the fatty acid composition,we examined eight types of pretreatment methods including:(a) drying the sample followed by direct methyl esterification using HCl-CH_3OH;(b) drying the sample followed by direct methyl esterification using H_2SO_4-CH_3OH;(c) drying the sample by ultrasonic extraction and methylesterification using HCl-CH_3OH;(d) drying the sample by ultrasonic extraction and methyl-esterification using H_2SO_4-CH_3OH;(e) fresh sample followed by direct methyl-esterification using HCl-CH_3OH;(f) fresh sample followed by direct methyl-esterification using H_2SO_4-CH_3OH;(g) fresh sample with ultrasonic extraction followed by methyl-esterification using HCl-CH_3OH,and(h) fresh sample with ultrasonic extraction followed by methylesterification using H_2SO_4-CH_3 OH.The results show that the δ~(13)C values from Groups a–e,g and h fluctuated within 0.3‰,and the δ~(13)C values of Group f were approximately 0.7‰ lower than the other seven groups.Therefore,the different sample pretreatment methods used towards the extraction of fatty acids from marine microalgae may result in different results regarding the stable carbon isotope ratios,and if necessary a correction should be applied.     

Cloud condensation nuclei activity of the Aitken mode particles near St. Petersburg,Russia

Aitken mode atmospheric particles largely control the formation and transformation of cloud systems, which in turn have an effect on their radiative properties. In this paper, a measurement technique for the cloud condensation nuclei (CCN) activity of monodisperse particles is described and the measurement data (results) obtained for monodisperse aerosol fractions with diameters of 60, 80, and 100 nm are presented. The measurements were performed during March and April 2014 at the urban background station located in a suburban area of St. Petersburg. The CCN concentration in the water-vapor supersaturation range of 0.1–1.1% and the cloud particle activation parameters were determined. The fraction of active particles capable to serve as CCN is found to be less than 33%, which is characteristic of anthropogenic aerosols containing hydrophobic organic components. Based on the measurement data, the hygroscopicity parameter κ characterizing the chemical composition effect on condensational properties of particles has been determined. During the measurement campaign, the value of the hygroscopicity parameter varied between 0.1 and 0.8. The lower limit of κ corresponds to organic species and its higher values occurs due to presence of hygroscopically active inorganic species in particles. The average value of κ was estimated to be 0.34 ± 0.19, which is in good agreement with literature data obtained for megapolises and European continental aerosols.     

Peculiarities of the disturbance in the mesosphere composition and optical emissions caused by high-altitude discharges

The suggested equation system, including 267 chemical reactions and corresponding parametrizations of disturbances of the electric field and electron temperature, describes the dynamics of the mesosphere composition under the influence of high-altitude discharges (sprites and halos). Based on this system, the ionic disturbance, neutral components, and optical emissions of the night mesosphere caused by the sprites were modeled for a height of 77–85 km. Most attention was paid to the dynamics of disturbances of concentrations of electrons and O ₂ ⁺ , NO⁺, H₃O⁺, H₅O ₂ ⁺ , and N ₂ ⁺ typical of the studied heights. The major chemical reactions leading to the disturbance of ionic contents are determined and the relaxation dynamics of the chemical components is reviewed. The account of the excited atoms and molecules of nitrogen and oxygen allowed us to model the radiation of the sprite flash, calculate the volumetric velocity of the photon emission, and study the influence of the sprite on the neutral components of the mesosphere.     

Nature and evolution of ultrafine aerosol particles in the atmosphere

Results of experimental and theoretical studies of a poorly understood phenomenon, an intense emission of ultrafine (nanometer) aerosols (ENA), are reviewed. In the English-language literature, this phenomenon is commonly referred to as a nucleation burst. ENA events have been observed on all the continents and throughout the depth of the troposphere, with the number of corresponding publications growing steadily. Intense and long-lasting ENA events have been studied more or less comprehensively and in full detail for Northern Europe, with 60 to 70% of observations taken in a forest area in the presence of snow cover and 10 to 20% in coastal marine areas. Most often, ENA events occur during spring and fall, with 95% of cases in the daytime and under sunny calm conditions, typical of anticyclones. In ENA events, the concentration of nanoparticles initially grows rapidly to values of 10³–10⁵ cm^?3. One or two hours later, the so-called nuclei fraction with diameters D = 3–15 nm is produced. The appearance of the Aitken fraction D = 20–80 nm and the enlargement of aerosol particles inside the accumulation fraction D = 80–200 nm may occur during the following 4–6 h. Thus, the cycle of formation and growth of atmospheric aerosol particles in the size range from a few to hundreds of nanometers is reproduced over 6–8 h. A specific synoptic feature of ENA events over land is that they occur when the polar air is transported to measuring sites and the temperature difference between day and light is large. During ENA periods, the formation rate of condensation nuclei with a diameter of 100 nm increases 10-to 100-fold. Important factors of ENA genesis are the “aerosol” and “electric” states of the atmosphere. More intense ENA events occur at low concentrations of background aerosols in the presence of atmospheric ions of medium mobility with D = 2–3 nm. The international experiments ACE 1 and 2, BIOFOR 1, 2, and 3, ESUP 2000, QUEST, etc., have not yet provided any clear answers to the questions about physical and statistical dependences of the time of origin and duration of ENA and new particle characteristics on the solar and ionized radiation intensity and on the content of minor and biogenic gases. Models of new particle formation are discussed in the review.     

Variations of the aerosol concentration and chemical composition over the arid steppe zone of Southern Russia in summer

Variations in the surface aerosol over the arid steppe zone of Southern Russia have been measured. The parameters of atmospheric aerosol (mass concentration, both dispersed and elemental compositions) and meteorological parameters were measured in Tsimlaynsk raion (Rostov oblast). The chemical composition of aerosol particles in the atmospheric surface layer has been determined, and the coefficients of enrichment of elements with respect to clarkes in the Earth’s crust have been calculated. It is shown that, in summer, arid aerosols are transported from both alkaline and sandy soils of Kalmykia to the air basin over the observation zone. Aerosol particles in the surface air layer over this region have been found to contain the products of combustion of oil, coal, and ethylized fuel. These combustion products make a small contribution to the total mass concentration of atmospheric aerosol; however, they are most hazardous to the health of people because of their sizes and heavy-metal contents. A high concentration of submicron sulfur-containing aerosol particles of chemocondensation nature has been recorded. Sources of aerosol of both natural and anthropogenic origins in southern Russia are discussed.     

Theory of interaction intensities,buffer capacities,and pH stability in aqueous systems,with application to the pH of seawater and a heterogeneous model ocean system

The choice of convenient basic constituents for evaluating pH stability of aqueous systems is discussed, and two useful interaction parameters are defined and related to the buffer capacity: the interaction capacity, $\text{δ′}{}_{\mathrm{X,Y}}\text{=}\text{?}\text{p}\text{X}\text{?}\text{TOT}\text{Y}$, and the interaction intensity, $\text{δ}{}_{\mathrm{X,\; Y}}\text{=}\text{?}\text{p}\text{X}\text{?}\text{pTOT}\text{Y}$; for pH and TOTH, δ′_{H, H} = ?β_H^?1, where β_H is the pH buffer capacity. A method is presented for the computation of exact values of all interaction capacities and intensities through inversion of the Jacobian matrix of the system of non-linear equations describing the aqueous system. The major species of an aqueous system (H₂O, H⁺, solid phases, gases, and the most abundant solute species) are shown to constitute a useful set of basic constituents for evaluation of approximate pH buffer capacities according to a simple rule: the major-minor species rule for zeroth order pH-TOTH interaction. The concepts of buffering and pH-statting are examined and contrasted; it is demonstrated that the buffer capacity of an aqueous system cannot be infinite: it is limited by the concentration of solutes in solution. The effect upon pH of variations in constituents other than H⁺ is described in terms of first order interactions via complex formation and solid formation; approximate formulas for calculation are derived. Higher order interactions are derived from combinations of first order ones. The pH stability of the ocean system is examined in terms of an aqueous phase model including ion-association reactions and a heterogeneous model incorporating CO₂ in the gas phase, quartz, kaolinite, calcite, chlorite, and illite, in addition to the aqueous phase. There is an approximately three-fold enhancement of buffer capacity in the aqueous model as a consequence of ion-association. Only a few interaction pathways are of quantitative significance in establishing the buffer capacity. Results for the heterogeneous ocean model lend quantitative support to Sillén's notion of pH stability: the buffer capacity is about four hundred times greater than that of the aqueous phase model.     

Characterization of the proteinaceous matter in marine aerosols

Marine aerosols play a dominant role in the transfer of oceanic material to the atmosphere. Most marine aerosol originates when air bubbles burst at the sea surface ejecting material from the sea surface microlayer and bubble surface layers into the air. Concentrations of chemical compounds in these surface layers often differ from their concentrations in bulk water. We examined the enrichment of aerosols with proteinaceous matter and attempted to characterize the physical nature and sources of this matter. We measured concentrations of dissolved free (DFAA), dissolved combined (DCAA), and particulate (PAA) amino acids, transparent stainable particles (TSP), and bacteria and virus-like particles as carriers of protein, in natural and simulated aerosols. We also evaluated D/L ratios certain amino acids in all amino acid fractions.DFAA and DCAA enriched the aerosols we sampled by 1.2–20 times compared to bulk seawater; PAA enrichment was usually higher (up to 50-fold). Aerosols contained particles typical of seawater, e.g., microorganisms, organic debris, inorganic particles with adsorbed organic matter, but also a large number of semitransparent gel-like particles, which all contained amino acids. Some of these particles were probably scavenged from bulk water, but new particles produced as bubbles burst at the surface comprised at least 10% of total proteinaceous matter in the aerosol. D/L ratios of certain amino acid suggested that the particles were most likely made from dissolved polymers secreted by phytoplankton that were concentrated on bubble surfaces and in the microlayer. Examination with Alcian Blue (a dye that targets carbohydrates) and Coomassie Blue (a dye that targets proteins) showed that most TSP in the aerosols contained both proteins and polysaccharides. Microorganisms enriched the aerosols by up to two orders of magnitude, but contributed less than 4% to the total protein pool.     

Origin and distribution of hydrogen sulfide in the Yuanba gas field,Sichuan Basin,Southwest China

The Yuanba gas field in the Permian Changxing Formation (P₂c), which exhibits wide variations in its hydrogen sulfide (H₂S) concentration (1.20–12.16%), is a typical sour gas field in the northern Sichuan Basin. The sulfur-rich reservoir's solid bitumen (atomic S/C ratios are 0.032–0.142), and late calcite cement δ¹³C values, which are smaller than the δ¹³C values of the host dolostone, indicate that the H₂S originated from thermal sulfate reduction (TSR) and oil was involved in TSR. The gas souring index (GSI) of P₂c's gases is generally lower than 0.1. The ethane δ¹³C values increase as the GSI increases, although no obvious increase was observed in the methane δ¹³C values. The calcite cements' δ¹³C values (−15.36 to +4.56‰) in dolostone are heavier than the typical reported values, which implies that only limited heavy hydrocarbon gases were involved in TSR. No anhydrites developed in P₂c's reservoirs, and dissolved sulfate anions (SO₄²⁻) were mainly enriched during dolomitization. Insufficient dissolved SO₄²⁻ most likely caused the lower H₂S concentrations in the Permian to Triassic reservoirs in the northeastern Sichuan Basin compared to the Permian Khuff Formation in Saudi Arabia and the Jurassic Smackover Formation in Mississippi. Except for the SO₄²⁻ in residual water in paleo-oil zones, SO₄²⁻ from bottom water may also be involved in TSR; therefore, oil reservoirs with bottom water have more SO₄²⁻ and can produce more H₂S than pure oil reservoirs. This phenomenon may be the main cause of the great difference in the H₂S concentrations between reservoirs, while gravitational differentiation during late uplift most likely creates differences in H₂S concentrations in a single reservoir. Carbon dioxide (CO₂), which has a relatively heavy δ¹³C value (−3.9 to −0.3‰), may be the combined result of TSR, the balance between CO₂ and inorganic fluid systems, and carbonate decomposition.