Comparison of Alternate Reactants for pM Level Cobalt Analysis in Seawater by the Use of Catalytic Voltammetry

The analysis of Cobalt (Co) at low pM concentrations in seawater with Adsorptive Cathodic Stripping Voltammetry involves high concentrations of sodium nitrite (NaNO₂) to enhance the signal in an electrocatalytic reaction. In this study we found three substitutes for NaNO₂ that critically affected the sensitivity. Optimisation of a method with potassium bromate (KBrO₃) resulted in an excellent detection limit (0.9 pM) after a 90 s adsorption period. Reactant concentration and consumption were 10× reduced compared to protocols with NaNO₂ and reagent blanks were lower. Accuracy and precision were verified with SAFe intercalibration standards and the method was applied using open ocean seawater samples. The reaction mechanism is discussed and differences to NaNO₂ are shown.     

Simultaneous confidence and prediction bands in the certification of pressure-volume curves for the pore size analysis of solids by means of mercury porosimetry

The pore size analysis of solids is widely applied in chemical industries, materials engineering, ceramic production, environmental engineering, catalysis, chromatography, nanotechnology, and many other fields. In spite of several new methods used for determining the pore size distribution of meso- and macropores [see IUPAC Recommendations of 1994], mercury porosimetry has remained one of the most popular methods employed for the characterisation of porous materials. In this paper, a new way is described for the estimation of certified pressure-volume curves from experimental curves measured by different laboratories in connection with the certification of new reference materials for a comparatively low-pressure range of mercury intrusion (<2 MPa). Simultaneous confidence and prediction bands for the certified pressure-volume curves are constructed by bootstrapping.     

基于系统调用的实时IDS方案

给出一种基于进程系统调用的实时IDS方案.该方案选择网络服务进程(特权进程)作为系统的代表进行监测,使用隐马尔可夫模型(HMM)对系统行为进行模拟和测试,使用实时P(O|λ)值和近期对“某些重要文件”的读、写频率这两个条件作为判断系统是否遭受入侵的标准.实验和分析表明,该方案有较高的预报准确率和较小的时间开销.     

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.     

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.     

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。     

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.     

A miniature and field-applicable multipumping flow analyzer for ammonium monitoring in seawater with fluorescence detection

In this article, a simple, economic, and miniature flow analyzer for ammonium in seawater based on the solenoid micropumps is presented. A single reagent of sodium tetraborate, ortho-phthaldialdehyde (OPA), and sodium sulfite was used and optimized applying the modified SIMPLEX method. A special-made detection cell for fluorescence detection of the reaction product isoindol-1-sulfonat was made and combined with a commercial photomultiplier tube, a long-pass optical filter, and an UV-LED as excitation light source. A LOD down to 13 nmol/L was achieved. The fabrication and application of a miniature reaction coil heating device for reaction rate enhancement is further described. The system featured an injection frequency of 32 h⁻¹ at average standard deviation of 3%.