Sonochemical conversion of CO2 into hydrocarbons: The Sabatier reaction at ambient conditions

In this study, we investigated an alternative method for the chemical CO₂ reduction reaction in which power ultrasound (488 kHz ultrasonic plate transducer) was applied to CO₂-saturated (up to 3%) pure water, NaCl and synthetic seawater solutions. Under ultrasonic conditions, the converted CO₂ products were found to be mainly CH₄, C₂H₄ and C₂H₆ including large amount of CO which was subsequently converted into CH₄. We have found that introducing molecular H₂ plays a crucial role in the CO₂ conversion process and that increasing hydrogen concentration increased the yields of hydrocarbons. However, it was observed that at higher hydrogen concentrations, the overall conversion decreased since hydrogen, a diatomic gas, is known to decrease cavitational activity in liquids. It was also found that 1.0 M NaCl solutions saturated with 2% CO₂ + 98% H₂ led to maximum hydrocarbon yields (close to 5%) and increasing the salt concentrations further decreased the yield of hydrocarbons due to the combined physical and chemical effects of ultrasound. It was shown that CO₂ present in a synthetic industrial flue gas (86.74% N₂, 13% CO₂, 0.2% O₂ and 600 ppm of CO) could be converted into hydrocarbons through this method by diluting the flue gas with hydrogen. Moreover, it was observed that in addition to pure water, synthetic seawater can also be used as an ultrasonicating media for the sonochemical process where the presence of NaCl improves the yields of hydrocarbons by ca. 40%. We have also shown that by using low frequency high-power ultrasound in the absence of catalysts, it is possible to carry out the conversion process at ambient conditions i.e., at room temperature and pressure. We are postulating that each cavitation bubble formed during ultrasonication act as a “micro-reactor” where the so-called Sabatier reaction -$C{O}_2+4H_2\stackrel{\mathit{Ultrasonication}}{\to }C{H}_4+2H_{2}O$ - takes place upon collapse of the bubble. We are naming this novel approach as the “Islam-Pollet-Hihn process”.     

Dynamically Restructuring NixCryO Electrocatalyst for Stable Oxygen Evolution Reaction in Real Seawater

In the pursuit of long-term stability for oxygen evolution reaction (OER) in seawater, retaining the intrinsic catalytic activity is essential but has remained challenging. Herein, we developed a Ni_xCr_yO electrocatalyst that manifested exceptional OER stability in alkaline condition while improving the activity over time by dynamic self-restructuring. In 1 M KOH, Ni_xCr_yO required overpotentials of only 270 and 320 mV to achieve current densities of 100 and 500 mA cm⁻², respectively, with excellent long-term stability exceeding 475 h at 100 mA cm⁻² and 280 h at 500 mA cm⁻². The combination of electrochemical measurements and in situ studies revealed that leaching and redistribution of Cr during the prolonged electrolysis resulted in increased electrochemically active surface area. This eventually enhanced the catalyst porosity and improved OER activity. Ni_xCr_yO was further applied in real seawater from the Red Sea (without purification, 1 M KOH added), envisaging that the dynamically evolving porosity can offset the adverse active site-blocking effect posed by the seawater impurities. Remarkably, Ni_xCr_yO exhibited stable operation for 2000, 275 and 100 h in seawater at 10, 100 and 500 mA cm⁻², respectively. The proposed catalyst and the mechanistic insights represented a step towards realization of non-noble metal-based direct seawater splitting.     

High-precision measurements of seawater Pb isotope compositions by double spike thermal ionization mass spectrometry

A new method for the determination of seawater Pb isotope compositions and concentrations was developed, which combines and optimizes previously published protocols for the separation and isotopic analysis of this element. For isotopic analysis, the procedure involves initial separation of Pb from 1 to 2 L of seawater by co-precipitation with Mg hydroxide and further purification by a two stage anion exchange procedure. The Pb isotope measurements are subsequently carried out by thermal ionization mass spectrometry using a ²⁰⁷Pb–²⁰⁴Pb double spike for correction of instrumental mass fractionation. These methods are associated with a total procedural Pb blank of 28 ± 21 pg (1sd) and typical Pb recoveries of 40–60%. The Pb concentrations are determined by isotope dilution (ID) on 50 mL of seawater, using a simplified version of above methods. Analyses of multiple aliquots of six seawater samples yield a reproducibility of about ±1 to ±10% (1sd) for Pb concentrations of between 7 and 50 pmol/kg, where precision was primarily limited by the uncertainty of the blank correction (12 ± 4 pg; 1sd). For the Pb isotope analyses, typical reproducibilities (±2sd) of 700–1500 ppm and 1000–2000 ppm were achieved for ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁸Pb/²⁰⁴Pb, respectively. These results are superior to literature data that were obtained using plasma source mass spectrometry and they are at least a factor of five more precise for ratios involving the minor ²⁰⁴Pb isotope. Both Pb concentration and isotope data, furthermore, show good agreement with published results for two seawater intercomparison samples of the GEOTRACES program. Finally, the new methods were applied to a seawater depth profile from the eastern South Atlantic. Both Pb contents and isotope compositions display a smooth evolution with depth, and no obvious outliers. Compared to previous Pb isotope data for seawater, the ²⁰⁶Pb/²⁰⁴Pb ratios are well correlated with ²⁰⁷Pb/²⁰⁶Pb, underlining the significant improvement achieved in the measurement of the minor ²⁰⁴Pb isotope.     

流动注射法同时测定海水中氨氮和磷酸盐

采用流动注射法同时测定海水中氨氮和磷酸盐的含量。在优化的试验条件下,氨氮和磷酸盐的线性范围分别为0.25 mg·L-1和0.30 mg·L-1以内,检出限(3S/N)分别为0.42μg·L-1和0.56μg·L-1。氨氮和磷酸盐加标回收率分别在85.0%~103%和86.7%~103%之间,测定值的相对标准偏差(n=6)分别在0.43%~5.3%和0~4.1%之间。方法用于分析标准物质,测定结果与分光光度法的结果一致。     

Multiscale Structures to Describe Porous Media Part I: Theoretical Background and Invasion by Fluids

A porous medium with a broad pore-size distribution is described on the basis of the Multiscale Percolation System concept. The representative structure is the superposition of several constitutive elementary networks, of which mesh sizes are proportional to the diameter of the class of pores considered. To account for the contribution of each class to the connection of the medium, a recurrent building process, involving rescaling and superposition, is defined. This process leads to an equivalent monoscale network, involving elements representative of the various classes. Mercury intrusion at increasing pressure into a finite-size sample of this equivalent network is modelled. The inverse problem is solved, leading to the identification of the representative multiscale structure of a given material from the experimental intrusion curve.     

Pore space network characterization with sub-voxel definition

Morphological measurements in 3D for pore space characterization (connectivity pore-body/throat classification, shape factors, virtual fluid intrusion) are based on computed intensive digital-thinning operations for skeletonization and medial axis extraction from 3D digital images. We present an alternative method that is measurably faster and allows sub-voxel definition of the pore space network. The method allows extracting—based on morphological considerations only—the centered and shortest stream-lines—i.e., the paths—to follow in order to go through the pore space from one given point to another and to exit. In addition the method penalizes long and narrow pore-throats in favor of short stubby/ones—i.e., it has a built-in exemplification capacity. It exploits well-established mathematical methods successfully applied in medical endoscopy.     

Modeling and Analysis of Seawater Intrusion in the Coastal Aquifer of Eastern Cap-Bon, Tunisia

A numerical model that treats density-dependent variably saturated flow and miscible salt transport is used to investigate the occurrence of seawater intrusion in the Korba aquifer of the eastern coast of Cap-Bon in northern Tunisia. We examine the interplay between pumping regimes and recharge scenarios and its effect on the saline water distribution. More localized simulations are used to examine, in vertical cross sections, the effects of well location and soil type and the role of the vadose zone in possible remediation actions. The exploratory simulations suggest interesting interactions between the unsaturated zone and the saltwater–freshwater interface with possible implications for groundwater exploitation from shallow unconfined coastal aquifers, involving in one case feedback between seawater intrusion and the high pressure head gradients around the pumping-induced drawdown cone and in another case threshold-like interface displacement for tight soils such as clays. The data processing steps undertaken in this GIS and modeling study are described in some detail, and a critical assessment is given of the data availability and of the requirements for successful monitoring and modeling of seawater intrusion risks in heavily exploited coastal aquifers such as those found in the semi-arid regions of the Mediterranean basin. It is shown how, with the aid of GIS, reasonably reliable information can be assembled from maps, surveys, and other sources of geospatial and hydrogeological data, an approach that is necessary in the many regions of the world with acute water resource problems but with limited means for undertaking systematic data acquisition and environmental monitoring actions. Nonetheless the need for more concerted monitoring of relevant parameters and processes and of closer coordination between monitoring and modeling is stressed. An idea of the extent of over-exploitation of the Korba aquifer is obtained by examining the pumping and rainfall/infiltration data, and the simulation results support groundwater pumping as the mechanism for and seawater intrusion as the origin of the salt contamination observed in the soils and subsurface waters of the Korba plain.     

广饶县海(咸)水入侵灾害防治的水文地质环境研究

广饶县咸水入侵灾害的发生在于自然环境的脆弱性和社会经济环境的严峻性。本文分析了引起海(咸)水入侵的基本矛盾, 制定了防治咸水入侵灾害的对策和措施──水文地质环境调整方案。     

煤层底板原位综合测试及突水危险性评估

在实施井下钻孔水压致裂地应力测量的同时,评价岩层阻水性能,确定导升带高度,做到一孔多用。测试区实际观测表明,泥岩、粉砂岩、中砂岩、灰岩阻水性能由大到小,导升高度则由小变大,平均导升高度约32m; 地应力测量表明,该测试区原始地应力状态为SH＞Sv＞Sh,最大水平主应力方向NE至NEE。突水临界指数评价表明,-550m水平采煤工作面掘进时突水的可能性较大,应当采取防范措施。     

Preparation of modified MFI (ZSM-5 and silicalite-1) zeolites for potassium extraction from seawater

Modified nanosized MFI (ZSM-5 and silicalite-1) zeolites were successfully synthesized by a hydrothermal method using aluminum isopropoxide and tetraethylorthosilicate as the raw materials. The synthetic zeolites were characterized by X-ray diffraction, energy dispersion spectroscopy, and scanning electron microscopy. The ZSM-5 and silicalite-1 zeolites exhibited ellipse-like and cubic columns, respectively. The K⁺ ion-exchange equilibrium and ion-exchange capacity of the synthetic zeolites in seawater were investigated. The K⁺ ion-exchange of synthetic zeolites was rapid and reached an ion-exchange balance in approximately 20 min. The K⁺ ion-exchange capacity of ZSM-5 and silicalite-1 in seawater was 56.7 and 48.7 mg/g, respectively. The synthetic zeolites have high selectivity toward K⁺, and therefore, they can be used to selectively extract potassium from seawater.