On the use of poorly soluble hygroscopic substances for modification of warm clouds and fogs

From analysis of the relationships between the equilibrium state of condensation nuclei and the relative humidity, a conclusion is made concerning the preferred use of poorly soluble substances for the generation of artificial condensation nuclei (ACN) designed for modification of warm clouds and fogs with the purpose of their dissipation and precipitation formation. The advantage of poorly soluble substances over commonly used soluble salts is that the finely dispersed part of the spectrum of the poorly soluble ACN does not deliquesce and so is not involved in the formation of cloud droplets. For experimental testing of the conclusions, preference was given to cement, whose main soluble substance is calcium oxide with a solubility of about 1 g/l. The spectrum of dispersed cement particles was measured and compared with the spectra of pyrotechnic flares widely used for modification at present. The process of formation of the cloud droplet spectra was simulated in the aerosol chamber of the Institute of Experimental Meteorology by decreasing the preliminarily generated excess pressure. It was found in these experiments that, compared to the spectra of particles formed on background condensation nuclei, the introduction of dispersed cement leads to the broadening of spectra and to a decrease in the concentration of droplets. Even at the early stage of condensation, droplets with radii of ∼20 μm appear. In this case, no “overseeding” phenomenon is observed, which, for soluble substances, manifests itself in an increase in the concentration of cloud droplets with a large ACN concentration. These effects indicate that, according to the existing concepts about the mechanism of warm-cloud modification with hygroscopic substances, the introduction of poorly soluble ACN (in particular, dispersed cement) below the base of cumulus clouds should stimulate coagulation processes and accelerate rain-formation processes. Considerations are given that the introduction of poorly soluble ACN into the already existing cumulus or stratocumulus clouds or fogs should also result in the acceleration of precipitation-formation processes or cloud dispersal. Comparison of cement powder with the well-known means of warm-cloud and fog modification is carried out. Original Russian Text ? N.P. Romanov, A.S. Drofa, N.S. Kim, A.V. Savchenko, G.F. Yaskevich, 2006, published in Izvestiya AN. Fizika Atmosfery i Okeana, 2006, Vol. 42, No. 1, pp. 80–91.     

Some properties of surf-beats

Long ocean waves with periods of several minutes (surf-beats) were observed at a marine observation tower. We have analysed time series data of an envelope of incident swell, long period current velocity and surface elevation fluctuations. Current velocity was measued by an electromagnetic flow meter. Surf-beats amplitudeH ^(l) is shown to be proportional to 3/2 power of incident swell amplitudeH ^(s), and decreases with increase of depthh in proportional toh ^–1/2 such thatH ^(l) H ^(s) (H ^(s)/h)^1/2. Frequency energy density functionP _LL (f) of surface elevation had two dominant peaks whose frequencies were highly stable through the entire observational period. Cross-spectral analysis suggested that those peaks correspond to traveling edge waves caused by the excess momentum and mass flux in the surf zone. The forced long ocean waves predicted byLonguet-Higgins andStewart (1964) was ditected. Phase-shift and wave height of the wave with respect to those of incident swell envelope are shown to be in remarkable agreement with the predictions. However the forced long wave is only a minor component in the total energy of surf-beats. Current fields are shown to be largely composed of non-surface modes.     

2018年烟台四十里湾及其邻近海域网采浮游植物群落结构的时空变化

本文基于2018年5月（春季）、8月（夏季）、11月（秋季）和2019年1月（冬季）季度航次调查,采用冗余分析（RDA）和Bray-Curtis相似性聚类分析方法,讨论了烟台四十里湾及其邻近海域网采浮游植物丰度、优势种组成、多样性指数、均匀度指数的分布特征以及浮游植物与环境因子的关系。本年度调查共发现浮游植物4门69属116种,其中硅藻门50属85种,甲藻门15属27种,着色鞭毛藻门3属3种,未定类1种（三深碎裂藻,Ebria tripartita）。浮游植物丰度在8月份达到年度最高值,为2.89×10⁸cells/m³,秋季次之,春季最低,春、秋、冬季浮游植物丰度均为~10⁵cells/m³。硅藻门在4个季节中均占绝对优势,除春季出现甲藻门（夜光藻）优势种外,其余季节浮游植物优势种均为硅藻门。相邻季节浮游植物优势种更替明显,未出现4个季节共有的优势种。浮游植物多样性和均匀度指数均在夏季达到最低值,分别为1.58和0.31。RDA排序分析显示,不同季节影响浮游植物群落分布的环境因子不同,总体来讲,温度、溶解氧浓度、SiO₃^2-浓度和NO₃^-浓度对浮游植物的丰度和平面分布有显著影响。Bray-Curtis相似性聚类结果显示,2018年每个季节浮游植物群落分布均可分为两个类群,其分布受营养盐分布的影响较为明显。     

Formation of cloud microstructure during hygroscopic seeding

The evolution of cloud microstructure initiated by hygroscopic seeding is studied on the basis of numerical simulation of cloud formation in the initial stage of condensation. The influence of both physicochemical properties of atmospheric aerosol and atmospheric conditions controlling the cloud type on the microstructure of a developing cloud (without hygroscopic seeding) is analyzed. It is shown that cloud seeding with additional particles whose sizes exceed the characteristic size of atmospheric condensation nuclei leads to a decrease in the concentration of cloud droplets and an increase in their sizes. This result of cloud seeding represents a positive effect for stimulation of precipitation from convective clouds. It is shown that this positive effect is achieved if there are some relationships between the parameters characterizing the hygroscopic particles and the atmospheric conditions. In particular, the maximum effect of action can be achieved at some optimal concentration of seeded particles. The decrease in the concentration of cloud droplets because of hygroscopic seeding is compared to the results of numerical simulations performed by other authors with allowance for coagulation processes in clouds. It is shown that this decrease can serve as an estimate for the effectiveness of hygroscopic seeding as a means for artificial intensification of precipitation from convective clouds.     

Ionization of water in seawater

The ion product of water in seawater and the total activity coefficients of hydroxide and hydrogen ions were determined over the temperature range 2° to 35°C, and the salinity range 20‰ to 44‰. At 25°C and 35‰ salinity, the measured values are pK_W^SW = 13.20, f_OH = 0.22, f_H = 0.71 on the molar concentration scale.     

The Increase of Biogenic Sulfate Aerosol and Particle Number in Marine Atmosphere over the Northwestern North Pacific

During a cruise aboard the R/V Hakuho-maru in the northwestern North Pacific in the summer of 1998 the particle number concentrations and the major ionic components of size fractionated aerosols were measured to investigate the aerosol produced by marine biological activity. Continuous low concentrations of nitrate (<1.8 nmol m⁻³), similar to the marine air background level, were found over the northwestern North Pacific (40–45°N) and the Sea of Okhotsk (44–45°N). Over the Sea of Okhotsk, a high concentration of chlorophyll-a (5.4 mg m⁻³) in seawater was observed, and atmospheric concentrations of non sea-salt (nss-) sulfate (44 nmol m⁻³), methane sulfonic acid (MSA) (1.8 nmol m⁻³) and particle number in the size range of 0.1 < D < 0.5 μm (199 cm⁻³) were found to be 9, 7, and 2 times, respectively, higher than those in the background marine air. The increase in particle number concentrations mainly in the size range of 0.2 < D < 0.3 μm was likely caused by the increase of biogenic sulfate over the high productive region of the Sea of Okhotsk. In humid air conditions (R.H. > 96%), the increased biogenic sulfate that condensed the large amount of water vapor would not have sufficient solute mass to activate as cloud condensation nuclei (CNN) and would remain as aerosol particles in the marine air with frequent sea-fogs over the high productive region. Biogenic sulfate originating from dimethyl sulfide (DMS) would gradually grow into the CCN size and continuously supply a great number of CCN to the marine air in the northwestern North Pacific. This revised version was published online in July 2006 with corrections to the Cover Date.     

A FURTHER APPROACH TO THE ASSOCIATION OF H+ WITH CL-

The Various experimental results from potentiometric methods have shown that no clearand definite evidence of ion pair HCl° is formed in HCl or HCl-HClO_4 ageous solution.The K_(HC1)~* to be computed by means of a potentiometric method introduced by Johnson et al.     

Dissociation constants of protonated cysteine species in seawater media

The dissociation constants (pK₁, pK₂ and pK₃) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK₃ in the Na–Mg–Cl solutions have been attributed to the formation of Mg²⁺ complexes with Cys²⁻ anions

Mg²⁺ + Cys²⁻ = MgCys

The stability constants have been fitted to

after corrections are made for the interaction of Mg²⁺ with H⁺.The pK₁ seawater measurements indicate that H₃Cys⁺ interacts with SO₄²⁻. The Pitzer parameters β⁰(H₃CysSO₄), β¹(H₃CysSO₄) and C(H₃CysSO₄) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK₂ and pK₃ in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK₁, pK₂ and pK₃ that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

Calorimetric study of the thermodynamics of formation of MgSO4 and NaSO4− ion pairs at the ionic strength of seawater

The formation of the ion pairs MgSO₄ and NaSO₄^? was investigated calorimetrically at 0.75 M ionic strength, 25°C, 1 atm. Simultaneous determinations of enthalpy changes, ΔH₁⁰, and stability constants, K₁, were not possible, and values of K₁ determined independently had to be introduced for the calculation of ΔH₁⁰. The values of ΔH₁⁰ obtained were 1–3 kJ mol^?1 for MgSO₄ and 0 kJ mol^?1 for NaSO₄^?.     

Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

2011年胶州湾网采浮游植物群落结构及其环境影响因子

本文于2011年1-12月对胶州湾海域浮游植物进行了周年调查,获得了同步的温盐和营养盐数据,分析了浮游植物丰度、优势种类、多样性指数和季节变化特征及其与环境影响因子的关系。结果表明：共检出浮游植物108种（包括变种和变型）,其中硅藻门34属93种,甲藻门6属14种,金藻门1属1种。浮游植物主要由硅藻和甲藻两大类组成,其中硅藻占绝对优势,全年甲藻/硅藻比均小于0.08。优势种共有35种,夏、冬季优势种交替明显,全年几乎均出现的种类为圆筛藻（Coscinodiscus spp.）,旋链角毛藻（Chaetoceros curvisetus）和中肋骨条藻（Skeletonema costatum）。生态类型主要以广布种、广温近岸种、温带近岸种为主,也出现了少数暖水种和外洋种。浮游植物丰度分别在2月、4月和7月份达到峰值,其中4月全年最高,为591×10⁶cell/m³,2月是次高峰,数量为468×10⁶cell/m³,7月为172×10⁶cell/m³,秋季浮游植物丰度相对较低。本研究结果与胶州湾浮游植物典型双峰型变化不同。浮游植物群落多样性指数平均为2.4,秋、冬季节较高,春、夏季节偏低,水平分布上呈现湾外 > 湾口 > 湾内的趋势,均匀度平均值为0.26,分布趋势与多样性指数基本相同。由此可见,湾外浮游植物群落结构较湾口和湾内更为稳定,温度、硅酸盐、亚硝酸盐、硝酸盐、铵盐和磷酸盐对浮游植物丰度和群落结构存在明显影响。     

Heat budget in the Japan Sea

The long-term mean (31-year mean) surface heat fluxes over the Japan Sea are estimated by the bulk method using the most of the available vessel data with the resolution of 1^o×1^o. The long-term annual mean net heat flux is about –53 W m^–2 (negative sign means upward heat flux) with the annual range from 133 W m^–2 in May to –296 W m^–2 in December. The small gain of heat in the area near Vladivostok seems to indicate the existence of cold water flowing from the north. In that area in winter, the mean loss of heat attains about 200 W m^–2, and the Bowen's ratio is over the unity. The largest insolation occurs in May in the Japan Sea, and the upward latent heat flux becomes the largest in November in this area. The heat flux of Haney type is also calculated, and the result, shows that the constantQ ₁ has the remarkable seasonal and spatial variation, while the coefficientQ ₂ has relatively small variation throughout all seasons. Under the assumption of constant volume transport of 1.35×10⁶ m³s^–1 through the Tsugaru Strait, the long-term averages of the volume transport through the Tsushima and Soya Straits are estimated to be about 2.20 and 0.85×10⁶ m³s^–1 from the result of the mean surface heat flux, respectively.     

The relationship between seagrass (Posidonia oceanica) decline and sulfide porewater concentration in carbonate sediments

In this study we test the hypothesized negative relationship between seagrass status and porewater hydrogen sulfide (H₂S) levels, through a comparative analysis within a range of seven Posidonia oceanica meadows growing over carbonate sediments in the NW Mediterranean Sea around Mallorca Island. The studied meadows range from meadows growing on sediments with very low sulfide porewater concentrations (4.6 μM) to those growing over higher sulfide conditions (33.5 μM). Organic matter content, sulfate reduction rates and sulfide porewater concentrations in the sediments were determined concurrently with the assessment of demographic plant dynamics (specific mortality and net population growth rates). Sulfide porewater concentration increased with increasing organic matter content in the sediment, while net population growth decreased significantly with low increases of sulfide concentrations. Our results confirm the previously suspected vulnerability of seagrass meadows growing on carbonate sediments to increased sulfide levels. An excess of 10 μmols H₂S L⁻¹ porewater is identified to already conduce P. oceanica meadows to decline, which this study identifies, particularly, as strongly sensitive to sulfides. The results reported here suggest that even moderate increases in organic carbon inputs may lead to enhancement of dissolved sulfides and may be an important factor for seagrass status in these iron-depleted carbonate sediments from the Mediterranean Sea.     

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.     

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.     

Methane-dominated thermochemical sulphate reduction in the Triassic Feixianguan Formation East Sichuan Basin, China: towards prediction of fatal H2S concentrations

New sour pools have recently found in the Lower Triassic Feixianguan Fm carbonate reservoirs in the East Sichuan Basin in China with H₂S up to 17.4% by volume. A recent blowout from a well drilled into this formation killed hundreds of people as a result of the percentage concentrations of H₂S. In order to assess the origin of fatal H₂S as well as the cause of petroleum alteration, H₂S concentrations and the isotopes, δ³⁴S and δ¹³C have been collected and measured in gas samples from reservoirs. Anhydrite, pyrite and elemental sulphur δ³⁴S values have been measured for comparison. The high concentrations of H₂S gas are found to occur at depths >3000 m (temperature now at 100 °C) in evaporated platform facies oolitic dolomite or limestone that contains anhydrite nodule occurrence within the reservoirs. Where H₂S concentrations are greater than 10% its δ³⁴S values lie between +12.0 and +13.2‰ CDT. This is within the range of anhydrite δ³⁴S values found within the Feixianguan Fm (+11.0 to +21.7‰; average 15.5±3.5‰ CDT). Thus H₂S must have been generated by thermochemical sulphate reduction (TSR) locally within the reservoirs. Burial history analysis and fluid inclusion data reveal that the temperature at which TSR occurred was greater than about 130–140 °C, suggesting that the present depth-temperature minimum is an artifact of post-TSR uplift. Both methane and ethane were actively involved in TSR since the petroleum became almost totally dry (no alkanes except methane) and methane δ¹³C values become significantly heavier as TSR proceeded. Methane δ¹³C difference thus reflects the extent of TSR. While it is tempting to use a present-day depth control (>3000 m) to predict the distribution of H₂S in the Feixianguan Fm, this is an invalid approach since TSR occurred when the formation was buried some 1000–2000 m deeper than it is at present. The likelihood of differential uplift across the basin means that it is important to develop a basinal understanding of the thermal history of the Feixianguan Fm so that it is possible to determine which parts of the basin have been hotter than 130–140 °C.     

Structure and seasonal variability of the deep mean circulation of the East Sea (Sea of Japan)

The horizontal structure of deep mean circulation and its seasonal variability in the Japan/East Sea (JES) were studied using profiling float and moored current meter data. The deep circulation in the Japan Basin (JB) flows cyclonically, basically following f/H contours. The correlation between the directions of deep current and f/H contour increases as |▿(f/H)| increases, reaching remarkably high correlation coefficient (>0.8) values in steep slope regions in the JB. In contrast to the JB, the deep mean circulation in the Ulleung/Tsushima Basin (UTB) is generally weak and cyclonic accompanied by sub-basin-scale cyclonic and anticyclonic eddies. The UTB shows a poorer correlation between directions of deep current and f/H contours than other basins. The time-space averaged deep mean current is about 2.8 cm/s and the volume transport in the deep layer (800 m to bottom) in the JB reaches about 10 Sv (10 × 10⁶ m³s⁻¹), which is about four times greater than the inflow transport through the Tsushima Straits. A salient feature is that the amplitude of deep mean current in the JB reveals a remarkable seasonal variation with a maximum in March and minimum in October. The annual range of the seasonal variation is about 30% of the mean velocity, whereas that in the southern JES (UTB and Yamato Basin) is weak.     

On the influence of atmospheric chemical reactions on the ion composition of aerosol particles in the Baikal region

Monitoring data on the ion composition of aerosols and gas admixtures in the background and polluted atmosphere of the Lake Baikal region are presented. The ion composition and morphology of aerosols are affected by heterogeneous chemical reactions and variations in relative humidity. Two types of aerosol particles are revealed over this region. The fraction of solid particles recorded in most episodes includes primarily carbonates of alkaline and alkaline-earth metals. With increased atmospheric humidity, these particles are engaged in heterogeneous chemical reactions with gas-phase NH₃ and H₂SO₄, proceeding through the phase of watering. As a result, the composition of these aerosols is changed, and a fraction of aqueous H₂O/H₂SO₄/(NH₄)₂SO₄ aerosol particles of a different composition is formed. On the basis of a physical and chemical analysis of monitoring data on the aerosol composition and concentrations of gas admixtures, the average aerosol-size distribution of different types is estimated. For the first time, the mean acidity of aqueous aerosol particles is estimated.     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3 and SiO2(OH)2. A precision study at 25°C in a simplified seawater medium

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH⁻ was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 B 0.008 M and 2.5 -log[H⁺] 11.7, respectively. Within these ranges the formation of SiO(OH)₃⁻ and SiO₂(OH)₂²⁻ with formation constants log β₋₁₁(Si(OH)₄ SiO(OH)₃⁻ + H⁺) = −9.472 ±0.002 and log β₋₂₁(Si(OH)₄ SiO₂(OH)₂²⁻ + 2H⁺) = −22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with -log[H⁺] 10.7 their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.     

Chromium(VI) reduction by sulphur(IV) in aqueous solutions

The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔH_app of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression

−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]²