THE OLIGOCENE–MIOCENE MENILITE FORMATION IN THE UKRAINIAN CARPATHIANS: A WORLD‐CLASS SOURCE ROCK

This study investigates the hydrocarbon potential of Oligocene–Miocene shales in the Menilite Formation, the main source rock in the Ukrainian Carpathians. The study is based on the analysis of 233 samples collected from outcrops along the Chechva River in western Ukraine in order to analyse bulk parameters (TOC, Rock‐Eval), biomarkers and maceral composition. In Ukraine, the Menilite Formation is conventionally divided into Lower (Lower Oligocene), Middle (Upper Oligocene) and Upper (Lower Miocene) Members. The Early Oligocene and Early Miocene ages of the lower and upper members are confirmed by new nannoplankton data. The Lower Menilite Member is approximately 330 m thick in the study area and contains numerous chert beds and turbidite sandstones in its lower part together with organic‐rich black shales. The shales have a high content of silica which was probably derived from siliceous micro‐organisms. The TOC content of the shales frequently exceeds 20 wt.% and averages 9.76 wt.%. HI values range between 600 and 300 mgHC/gTOC (max. 800 mgHC/gTOC). The Middle Member contains thin black shale intervals but was not studied in detail. The Upper Member is about 1300 m thick in the study area and is composed mainly of organic‐rich shales. Chert layers are present near the base of the Member, and a prominent tuff horizon in the upper part represents a volcanic phase during shale deposition. The member grades into overlying molasse sediments. The average TOC content of the Upper Menilite succession is 5.17 wt.% but exceeds 20 wt.% near its base. Low T_max and vitrinite reflectance measurements for the Lower (419°C and 0.24–0.34 %R_r, respectively) and Upper (425°C and 0.26–0.32 %R_r, respectively) Menilite Member successions indicate thermal immaturity. Biomarker and maceral data suggest a dominantly marine (Type II) organic matter input mixed with varying amounts of land‐plant derived material, and indicate varying redox and salinity conditions during deposition. Determination of the Source Potential Index (SPI) shows that the Menilite Formation in the study area has the potential to generate up to 74.5 tons of hydrocarbons per m². The Chechva River outcrops therefore appear to have a significantly higher generation potential than other source rocks in the Paratethys realm. These very high SPI values for the Menilite Formation may explain why a relatively small area in Ukraine hosts about 70% of the known hydrocarbon reserves in the northern and eastern Carpathian fold‐thrust belt.     

Agronomical evaluation of phosphate fertilizer as a nutrient source of phosphorus for crops: Isotopic procedure

The agronomic effectiveness of P fertilizers, as sources of phosphorus for crops, was evaluated using the quantities, P_f, of phosphorus taken up byLolium perenne grown on 14 soils during greenhouse experiments in pot cultures. The P_f quantities were determined using³²P-labelled fertilizers. Data were analysed using a new concept: the Isotopic Relative Agronomic Effectiveness (IRAE). The IRAE value was defined as the ratio of the P_f quantity, taken up by a crop, of a tested fertilizer over the P_f quantity, taken up by a crop, of a fertilizer used as standard. In our experiments diammonium phosphate (DAP) was used as standard P fertilizer and two rock phosphates, the North Carolina rock phosphate (NCPR) and a calcium-iron-aluminium phosphate (Phospal), were tested. As a linear relationship between P_f(NCPR) quantities and P_f(DAP) quantities was obtained, with r² = 0.95, when the application rates increased from 15 mgP (kg soil)^–1 to 200 mgP (kg soil)^–1, it is conciuded that IRAE values for a given fertilizer, other than the standard fertilizer, could be determined with a single rate of application. As regards soil pH in the range 4.7 to 8.2 the IRAE_NCPR is related to soil pH by a curvilinear relationship: log IRAE_NCPR = –(0.44) pH + 4.05 with r² = 0.89. The average of IRAE_phospal values was 0.15 with a standard error = 7% irrespective of soil pH. Then a logarithmic relationship was obtained between IRAE values of the two tested fertilizers and their water P-solubility determined at the soil pH where they were applied.     

The determination of phosphate availability for some less conventional phosphate fertilisers

More than in the case of the other major fertiliser elements the performance of phosphorus in fertilisers in dependent on the state of chemical combination of the element. As distinct from typical American practice where fully acidulated fertilisers are emphasised, some other countries have moved in part to production of materials of less than full acidulation where some reliance is placed on the reactivity of the original phosphate rock. Solutions of various aliphatic acids and their salts have been used as tests for the availability of phosphorus in fully acidulated fertilisers and, to a degree, for phosphate rocks themselves. Less than fully acidulated products are at present assessed in the same way as fully acidulated materials, but in this and other evaluations problems and anomalies arise which are discussed within the framework of a number of fertiliser systems. Analytical data are adduced which illustrate the effects of some extraneous cations on the results achieved which conflict with some previous opinions. Research towards a fuller understanding of the subject is suggested.     

A discussion of the methods for comparing the relative effectiveness of phosphate fertilizers varying in solubility

Because various phosphate (P) fertilizers differ widely in their solubility, it is commonly observed that crop response to P fertilizers varies under the same soil and crop conditions. Furthermore, a major problem encountered in the methods for determining the relative effectiveness (RE) of water-insoluble P fertilizer (e.g., phosphate rock) with respect to water-soluble P fertilizers, e.g., single superphosphate (SSP) and triple superphosphate (TSP), is that their growth response curves are usually nonlinear and often do not share a common maximum yield. In this paper, we review and discuss the advantages and disadvantages of the three most commonly used methods for calculating the RE of phosphate rock with respect to TSP (or SSP). The three methods are vertical comparison, horizontal (substitution rate) comparison, and linear-response comparison.     

A comparison of methods for measuring the effect of level of application on the relative effectiveness of two fertilizers

The effectiveness of a slowly soluble source of phosphate relative to a soluble source may decrease with increasing levels of application. This may cause yields to approach a lower asymptote. Four methods for measuring this effect are compared using field experiments in which a calcined rock phosphate (Calciphos) was compared with superphosphate for growth of subterranean clover. The methods were: subjective estimates using a hand drawn calibration curve; objective estimates using a fitted calibration curve; objective estimates using the fit of separate response curves; and objective estimates from the fit of a common response surface in which relative effectiveness was related to level of application. The role of these four methods differs. The first method, though often informative, is suitable only for an initial inspection of the data. The other three methods may all be useful for analysis but the fourth method was the most general. It gave the most sensitive statistical test and had the further advantage that it was a direct test of the hypothesis. All four methods showed that the relative effectiveness of Calciphos decreased with increasing levels of application.     

Optimising P2O5 availability for fertilizer use,by direct treatment of apatite with hydrochloric or nitric acids

Hydrochloric and nitric acid treated apatite is not directly used as a fertilizer because of the hygroscopic character of the products. Another problem arises from the volatility of these acids and that acidulated product undergo reversions during drying with loss of the acid. We have found that apatite beneficiated with hydrochloric and nitric acids dried at an optimum temperature ~120°C has high available phosphorous. The products can be stored in the solid form in sealed polythene bags.Sumanasekara Chair in Natural Science     

Recent Advances in Calcium-Based Anticancer Nanomaterials Exploiting Calcium Overload to Trigger Cell Apoptosis

Calcium ion is vital for the regulation of many cellular functions and serves as a second messenger in the signal transduction pathways. Once the intracellular Ca²⁺ level exceeds the tolerance of cells (called Ca²⁺ overload), oxidative stress, mitochondrial damage, and cell/mitochondria apoptosis happen. Therefore, Ca²⁺ overload has started to be deeply exploited as a new strategy for cancer therapy due to its high efficiency and satisfactory safety. This review aims to highlight the recent development of Ca²⁺-based nanomaterials (such as Ca₃(PO₄)₂, CaCO₃, CaO₂, CaH₂, CaS, and others) able to trigger intracellular Ca²⁺ overload and apoptosis in cancer therapy. The intracellular mechanisms of varied Ca²⁺-based nanomaterials and the different types of strategies to enhance Ca²⁺ overload are discussed in detail. Moreover, the design of more efficient Ca²⁺ overload-mediated cancer therapies is prospected mainly based on 1) the enhanced cellular uptake by surface modification and morphology optimization of nanomaterials, 2) the accelerated Ca²⁺ release from nanomaterials by increasing the intracellular H⁺ level and by photothermal effect, and 3) the overload maintenance by Ca²⁺ efflux inhibition, Ca²⁺ influx promotion, or promoting Ca²⁺ release from the endoplasmic reticulum.     

磷酸盐玻璃中Er~(3+)离子的光跃迁和激光作用

给出了Li-Al磷酸盐玻璃中Er~(3+)离子发射特性(Ar、σ_ρ、β、τ_γ)的计算结果。报道了Cr~(3+)→Yb~(3+)→Er~(3+)的一种有效能量转移,并获得了室温下3J1.54μm波长的激光输出。     

Stabilization of Amorphous Calcium Carbonate with Nanofibrillar Biopolymers

Calcium carbonate is the most abundant biomineral that is biogenically formed with a vast array of nano and microscale features. Among the less stable polymorphs present in mineralized organisms, the most soluble, amorphous calcium carbonate (ACC), formed in chitin exoskeletons of some crustacea, is of particular interest since aqueous stability of isolated ACC is limited to a few hours in the absence of polyanions or magnesium. Here the influence of a selection of biopolymer gels on the mineralization of calcium carbonate is investigated. Mineralization is achieved in all biopolymers tested, but is particularly abundant in collagen hydrogels, in which a significant proportion of the calcium carbonate (≈18%) is found to be amorphous. In dense collagen gels, this amorphous fraction does not crystallize for up to six weeks in deionized water at room temperature. The reason why collagen in particular should stabilize this phase remains obscure, although the results suggest that the fiber diameter, fiber spacing, and the amphoteric nature of collagen fibers are important. Upon immersion in phosphate containing solutions, the calcium carbonate present within the collagen hydrogels is readily converted to carbonated hydroxyapatite, enabling the formation of a stiff bone‐like composite containing 78 wt% mineral, essentially equivalent to cortical bone.     

PBGA焊接开裂失效原因分析及改善

由于PBGA组件点位于四件与PCB之间,焊点的检查和检修成本很高,控制PCB组件焊接失效显得尤为重要。文章通过对焊接失效的焊盘镍层、金层结构进行了SEM、X-RAY分析导致焊接失效产生的主要原因,并针对此现象进行控制与改善。