Miniaturized sensor module for in-situ control of waters

A new sensor module is developed for the in-situ control of waters, especially surface waters. Complex miniaturized sensor technology is used for the determination of the parameters pO₂, pH, pNO₃, pCl, pPO₄, pNH₃ or pNH₄ and conductivity. Miniaturization of sensors results in small sample volumes and small volumes of calibration solution required. Results of testing this sensor module are described. The special features of this apparatus are its compact construction and its optimum functioning capability under flow conditions.     

Miniaturized sensor module for in-situ control of waters

A new sensor module is developed for the in-situ control of waters, especially surface waters. Complex miniaturized sensor technology is used for the determination of the parameters pO₂, pH, pNO₃, pCl, pPO₄, pNH₃ or pNH₄ and conductivity. Miniaturization of sensors results in small sample volumes and small volumes of calibration solution required. Results of testing this sensor module are described. The special features of this apparatus are its compact construction and its optimum functioning capability under flow conditions. Received: 2 February 1998 / Revised: 30 March 1998 / Accepted: 18 April 1998     

Carbonic Anhydrase Facilitated CO2 Diffusion Studied by Means of an Ammonia Sensing Urease Electrode

Abstract

In the present work the influence of carbonic anhydrase (CA) on the gaseous exchanges of CO₂ and NH₃ in a buffered solution has been studied by means of a potentiometric technique involving the use of an urease sensor, whose sensing element was a commercial pNH₃ gas sensing electrode. As pointed out in previous works, suitable experimental conditions were chosen in order to have a speed of CO₂ diffusion sharply enhanced by CA. In particular the analytical aspect of NH₃ production from a buffered urea solution, in the presence and in the absence of CA, is considered.

The results obtained in the present work indicate a further possible application of this system to the study of living organism and tangibly support all the previous studies presented on this topic.     

Effect of solution pH on the stability of mixed silica -alumina suspension in the presence of polyacrylic acid (PAA) with different molecular weights

The influence of solution pH (in the range 3–9) on mixed silica-alumina suspension in the absence and presence of polyacrylic acid (PAA) was studied. The composition of the adsorbent was SiO₂ (97%) and Al₂O₃ (3%). The turbidimetry method was applied to record changes in the stability of the investigated systems as a function of time. It was shown that the suspension without the polymer is less stable at pH 3, whereas at pH 6 and 9, the systems were stable. PAA with molecular weights 100 000 and 240 000 at pH 3 (improvement of system stability conditions) and PAA 2 000 at pH 6 (deterioration of suspension stability) have a great effect on the silica-alumina suspension stability. The stabilization-flocculation properties of polyacrylic acid are a result of a specific conformation of its chains on the solid surface where it depends on the solution pH and the polymer molecular weight.     

Influence of solution pH on stability of aluminum oxide suspension in presence of polyacrylic acid

The effect of solution pH and molecular weight of polyacrylic acid (PAA) on its adsorption as well as on stabilization-floculation properties of the colloidal Al₂O₃ and electrolyte solution systems was studied. The measurements showed that at pH = 6, the presence of the polymer of molecular weight 2?000 and 240?000 does not change stability of Al₂O₃ suspension. However at pH =3 and 9 the effect of polyacrylic acid is significant. At pH = 3 it creates destabilization of the suspension while at pH = 9 PAA it improves significantly the stability of Al₂O₃. It was shown that the increase in solution pH affects conformation of adsorbed macromolecules which causes the decrease in PAA adsorbed amount and thickness of polymer adsorption layer. By comparing the values of diffusion layer and surface charges, main effects responsible for the decrease in surface charge and ζ potential of the solid in the presence of the polymer as well as suspension stability were determined.     

Random-Walk Aggregation Phenomena in Solid Bimodal Liquid Dispersions: Transition to Nondeterminism from Si3N4to Si3N4+ Al2O3Aqueous Systems

This paper, which is based on another recent work, (Mezzasalma, S. A.,Phys. Rev. E55(4), (1997)) deals with experiments and theory concerning an aqueous dispersed system formed from silicon nitride (Si₃N₄), alumina (Al₂O₃), and mixed silicon nitride + alumina (Si₃N₄+ Al₂O₃) solid agglomerates. From titration data applied to a thermodynamic equilibrium condition, the minimum number of each agglomerate species and their maximal average dimensions have been derived as functions of the aqueous solution pH. These parameters are of the order of, respectively, (1–2) μm for Si₃N₄and Al₂O₃agglomerates and (20–50) μm for the mixed agglomerates. The numbers of solid particles of all species are poorly correlated with changes in pH of the liquid phase. This behavior has been interpreted as intrinsically related to the complexity of the system which, due to the many interactions among the different species, probably becomes nondeterministic. In order to describe such behavior a probabilistic approach has been developed. The probability of finding a given solid agglomerate number within a scatter band varies with the suspension pH. Furthermore, the scatter band amplitude becomes negligible near the isoelectric point. Accordingly, only the numbers of aggregates derived in the neighborhood of the isoelectric point are predictable.     

Effect of Complexation on the Zeta Potential of Titanium Dioxide Dispersions

Abstract

The present paper deals with the surface charge properties and the dispersion stability of an aqueous titania suspension. Generally the titania powder surface is negatively charged. The dispersion stability of TiO₂ suspension is governed by the value of zeta potential. The zeta potential was measured as a function of barium acetate and zinc acetate concentrations, at pH 6.0, and the addition of electrolytes caused sharp decrease of surface charge. Ethylenediaminetetraacetic acid (EDTA) was used to chelate the bivalent metal ions, so that the charge of counterions was reduced. The complexation of bivalent counterions favors the increase of the negative zeta potential and the dispersion stability of aqueous TiO₂ suspension.     

Electrochemistry of solutions in liquid ammonia. Part VII. The use of glass electrodes for ammonium and sodium cations as ion-selective sensors at −40 °C

The behavior of Li/La glass electrodes as specific ion sensors for NH ₄ ⁺ and Na⁺ cations in liquid ammonia solutions at –40°C has been assessed using concentration cells with transference. The measurement of emf's of cells with very high resistances due to glass at –40°C has been overcome partly by the use of thinly blown Li/La glass and mainly through the design and use of a floating shield emf measuring system. For solutions of NH₄NO₃, NH₄I, NH₄BF₄, and NH₄Cl almost linear pNH₄ vs. emf responses were observed between pNH₄ 0 and 5; for NH₄NO₃ solutions the slope (40±1 mV/pNH₄) was invariant for substantial increases in Na⁺ concentrations. Solutions of NaNO₃, NaCN, NaClO₄, NaNCS, NaN₃, and NaNO₂ gave almost linear pNa vs. emf responses but the slopes were markedly dependent upon the NH ₄ ⁺ concentration. Estimates of the mean molal ion activity coefficients for nitrate solutions were obtained from earlier transference data: ±(NaNO₃)=0.14±0.02 and ±(NH₄NO₃)=0.30±0.03 at 10^– molal concentration in fair agreement with earlier data.     

The Spectrophotometric Investigation of Nonionic Polymer Adsorption (Polyethylene Glycol (PEG), Polyethylene Oxide (PEO) and Polyvinyl Alcohol (PVA)) Influence on the Alumina Suspension Stability – Effects of Polymer Type,its Molecular Weight and Solution pH

The effect of nonionic polymer adsorption on the stability of alumina (Al₂O₃) in the pH range 3–9 was examined. The influences of polymer type and its molecular weight, as well as solution pH, were studied. The following macromolecular substances were used: polyethylene glycol (PEG), polyethylene oxide (PEO) and polyvinyl alcohol (PVA). The spectrophotometry method was applied to obtain the stability curves (dependence of suspension absorbance vs. time). The obtained results indicate that the addition of the polymer influences alumina suspension stability. The addition of the polymer at pH 3 improves the stability conditions of investigated systems. At pH = 6 the decrease of Al₂O₃ suspension stability (except PEG 2 000) was obtained. On the other hand, at pH 9 the presence of polymer improves the stability properties of the alumina. The higher the molecular weight of the polymer, the more pronounced effects were observed. Moreover, adsorption of polyvinyl alcohol whose macromolecules contain ionizable acetate groups causes greater changes in alumina suspension stability in comparison to the systems containing polyethylene glycol and polyethylene oxide.     

Stability of Colloidal Silica Modified by Macromolecular Polyacrylic Acid (PAA) – Application of Turbidymetry Method

The effect of anionic polyacrlic acid (PAA) adsorption on fumed silica (SiO₂) surface on suspension stability was studied. The turbidymetry method was applied to monitor the changes in the suspension stability (using apparatus Turbiscan Lab^Expert with cooling module TLAb Cooler). PAA macromolecules contain dissociable carboxyl groups, therefore, all measurements were carried out at three pH values: 3, 6 and 9. Analysis of obtained transmission and backscattering curves and Turbiscan Stability Indexes (TSI) allowed determination of the most probable mechanism of the stability of the studied systems. The PAA adsorption has the greatest impact on the silica suspension stability at pH 3 (significant improvement of its stability). On the other hand, the presence of polyacrylic acid at pH 6 causes a noticeable deterioration of system stability conditions. At pH 9, polymer minimally influences the stability of SiO₂ suspension.     

Influence of Electrolytes on the Thixotropy of Ferric Aluminum Magnesium Hydroxide‐Montmorillonite Suspensions

Abstract

The thixotropy of suspensions consisting of ferric aluminum magnesium hydroxide (Fe‐Al‐Mg‐MMH) and Na‐montmorillonite (MT) is examined with special emphasis on the influence of electrolytes. When NaCl or MgCl₂ is added into the Fe‐Al‐Mg‐MMH/MT suspension, the thixotropy of the suspension may change (if positive) from positive and complex into negative, but NaCl or MgCl₂ can't alter the thixotropic type of a negatively thixotropic suspension. When AlCl₃ was added to positive thixotropic system can be transformed to a complex one, whereas a complex and negative thixotropic suspension remains unchanged, for additions less than 0.01 mol/L; when the addition level of AlCl₃ increases, all types of thixotropic systems are changed to non‐thixotropic. In addition, NaCl and MgCl₂ make the initial viscosity measured after cessation of intensive shearing increase, but the value of the viscosity decreased rapidly with time. The equilibrium viscosity of the suspension decreased gradually with increasing concentrations of NaCl and MgCl₂ in the suspension. With increasing concentration of AlCl₃, the equilibrium viscosities of the positive thixotropic suspension and the complex thixotropic suspension increase at first, but decrease later, and the equilibrium viscosity of negative thixotropic suspensions decrease gradually.     

Electrophoretic deposition of Al2O3/ZrO2 layer with controllable thickness in ethanol medium

ZrO₂ toughened Al₂O₃ (Al₂O₃/ZrO₂) ceramic layers with required thickness were prepared by electrophoretic deposition (EPD) method using ethanol suspensions with stabilizing agent of polyethyleneimine (PEI) under constant-voltage mode in this paper. The deposition of Al₂O₃/ZrO₂ ceramic powders occurred on the titanium alloy cathode. A stable suspension with 1wt% PEI in ethanol at pH 5 was prepared in terms of the zeta potential and sedimentation of the suspension. The effects of the suspension concentration, applied voltage, deposition time and processing method of titanium alloy cathode on the coating thickness and morphology were investigated. The deposition layers on titanium alloys with smooth surfaces and thickness of 0.35?C1.2 mm could be obtained by adjusting the aforementioned parameters. In addition, after being sintered at 1500°C for 3 h in air atmosphere, ZrO₂ toughened Al₂O₃ ceramic layers became smooth and dense.     

Effect of Conditions on the Dispersibility of ZrB2 Particles

ZrB₂@A1(OH)₃‐Y(OH)₃ core‐shell composite particles are synthesized by co‐precipitation method for strengthening the antioxidation of ZrB₂ at high temperature. To reach better A1(OH)₃‐Y(OH)₃ composite shell and higher coating ratio on the ZrB₂ particles surfaces, ZrB₂ particles must be adequately dispersed in the ZrB₂ suspension during the coating process. The dispersibility of ZrB₂ particles under different conditions is investigated by the sedimentation method. Through test and analysis, the optimum conditions of the dispersibility of ZrB₂ particles in the ZrB₂ suspension are sedimentating for 15 minutes, ultrasonic dispersion for 10 minutes, the lower ZrB₂ concentration, pH=9, the dispersant content for the 2% volume of ZrB₂ suspension, and using the polyelectrolyte dispersant, respectively.     

Comparison and Evaluation of Extraction Media and Their Suitability in a Simple Model to Predict the Biological Relevance of Heavy Metal Concentrations in Contaminated Soils

Abstract

The concentrations of heavy metals in agricultural soils are increasing gradually from various diffuse sources. The metals can transfer from contaminated soils into the growing plants or may affect the respiration rate of soil microorganisms.

In the first part of this paper, the following simple model to predict the biorelevant metal concentration in anthropogenically or artificially contaminated soils is reported: log M_p = α + β log [M_NaNO3] log M_R = α' + β' log [M_NaNO3] log M_P = log Metal concentration in test plant (mg/kg dry weight) log M_R = log percent Redution in the respiration or enzyme activity [M_NaNO3] = Metal concentration in NaNO3-soil extract (mg/kg soil) α and β & α' + β' = Intercepts and slopes of the linear regression lines.

The model has been tested in laboratory experiments, in growth experiments either in a greenhouse or in the field. Also, an attempt is made to present a theoretical interpretation.

Critical concentrations are calculated with the help of the relationship between metal concentration in soil solution [M_NaNO3] and metal concentration in plants. The critical concentration, which is able to induce either phyto- or zootoxic concentrations in the plant parts (productive or vegetative) or reduce their growth or to reduce significantly the growth of soil microorganisms, are found to be uniform in a wide range of soils (pH 3 to 8 and CEC 10–50 millimol/100g soil), the critical concentrations of NaNO₃ in soil extracts are comparable with the values obtained with plant growth experiments in nutrient solution and also with the concentrations obtained from soil respiration experiments reported in literature.     

31P NMR Measurement of Intracellular pH in Bacillus FTU

Abstract

The ability of alkalotolerant bacterium Zacillus FTU to maintain intracellular pH was studied in the wide range of extracellular pH: 6.5–11, by means of ³¹P NMR. Bacillus FTU is an obligatory aerobic microorganism, possessing a high speed of oxygen consumption, that is why it was especially important to provide sufficient oxygen supply during the entire period of measurement. We have worked out a special glass filter insert for the NMR sample tube which allowed for uniform air supply in the cell suspension. The viability of the cells was checked by ATP level analysis Since in the case of Bacillus FTU ATP content if highly sensitive to the quantity of oxygen. The endogeneous P₁ was used as a pH indicator. The level of P_i is extremely high in Bacillus FTU-around 70–30 mM, that's why it was possible to use relatively low concentration of cells in the suspension to obtain sufficient NMR sensitivity (approximately 5–7; of intracellular volume). Special procedure was employed to obtain a calibration curve: we used gramicidin in the concentration 10 pM to equilibrate in-tra- and extracellular pH; the former being measured by ³¹P NMR and the latter-by pH-meter. Bacillus FTU in energized state showed the ability to maintain constant intracellular pII (approximately 8.0–8.5) in the range of extracellular pH from 7.3 till 10.5, which agreed with the pH range of the cell growth. Thus, the obtained data support the idea of intracellular pH being of vital importance for cell metabolism.     

Effect of Mixing Entropy on the Static Yield Stress of a Liquid Dispersion of Solid Particles: Comparison between Si3N4and Ca3(PO4)2Aqueous Suspensions

Experimental measurements of the static yield stresses τ of silicon nitride (SN, Si₃N₄) and α-tricalcium phosphate (TCP, α-Ca₃(PO₄)₂) aqueous dispersions have been performed for different pH values of the liquid medium and, as a result, the two τ vs pH behaviors are quite different. In agreement with the DLVO theory, the static yield stress value for silicon nitride is maximal at the isoelectric point of the slurry (pH_iep^(SN)= 8.0 ± 0.1) and, for higher and/or lower suspension pH values, it decreases progressively. On the other hand, in tricalcium phosphate dispersed systems, the maximum value of τ is not observed at the isoelectric point (pH_iep^(TCP)= 6.7 ± 0.1) but two relative maximum values, τ_aand τ_b, are observed for two suspension pH values in the acid/basic environments, namely, for pH pH_iep^(TCP). First, displacements of the pH from the isoelectric point in both environments are accompanied by an increase in τ; second, after the maximum τ values have been reached, the static yield stress decreases with the increase in the [H⁺]/[OH⁺] ions in the solution. It is shown that this phenomenon can be interpreted as an effect of the mixing entropy relative to the solid TCP aggregates, which is very sensitive to the suspension pH. Phenomenological and theoretical explanations are developed, respectively, by a heuristic recasting of the Hamaker expression for the London–van der Waals forces and by a relationship between the static yield stress and the number of solid aggregates; this relation is based on recently proposed methods for investigating the agglomeration/adsorption phenomena in a dispersed system.     

pH-dependent Co(II) assemblies from achiral 2-benzothiazolylthioacetic acid: crystal structures,symmetry breaking,and magnetic properties

Based on an achiral 2-benzothiazolylthioacetic acid (HL) ligand, three Co(II) coordination compounds, {[Co(L)₂(H₂O)₃]·H₂O}_n (1), [Co(L)₂(H₂O)₂]_n (2), and [Co(L)₂(H₂O)₄]·2H₂O (3), were obtained under different pH environments. Compound 1 possessing an interesting chiral 1-D helical double chain was synthesized with pH of 5.0~6.5, and the chiral symmetry breaking has been probed by single-crystal X-ray diffraction and circular dichroism spectroscopy. Switching pH to 4.0~5.0 and 3.0~4.0 resulted in achiral 2 and 3, respectively. Compound 2 has a 1-D chain structure and 3 is mononuclear.     

Model study of acid rain effect on adsorption of trace elements on soils using a multitracer

Using a radioactive multitracer and model acid rain (HCl or H₂SO₄ solution), batch experiments were performed to examine the pH effect on the adsorption-desorption equilibrium of 16 elements on soils as a model study of an acid rain effect. Kaolin, black soil (original and with organic matter almost removed) and Kureha soil (original and with organic matter almost removed) were used as adsorbents. Characteristic dependence on the pH value of the suspension was observed for the adsorption of the elements on kaolin and the soils. The results of this model study indicate that acid rain decreases the retention of cations, while it increases or does not change the adsorption of anions on soils. Organic matter in soils has a positive effect on the extent of adsorption of most elements investigated.     

Crystal structure and solid state IR-LD analysis of a mononuclear Cu(II) complex of 4-aminopyridine

A new mononuclear Cu(II) complex of 4-aminopyridine (4AP), [Cu(4AP)₄]Cl₂·2CH₃OH (1), was obtained and structurally characterized by single-crystal X-ray diffraction methods. The complex is square-planar involving four monodentate 4AP molecules coordinated through the N_py atoms. A solid-state linear-dichroic spectroscopic analysis (IR-LD) as a suspension in a nematic liquid crystal was carried out over the 4000–400?cm^?1 range and determined stereochemical parameters compared crystallographic data. Detailed IR characteristics are reported.     

Assessment of single extractions for the determination of mobile forms of metals in highly polluted soils and sediments--analytical and thermodynamic approaches

Highly polluted forest/tilled soils and stream sediments from a mining and smelting area were subjected to single-extraction procedures to determine the extractable contents of Cd, Cu, Pb, and Zn. The results obtained from four widely used operationally defined single extraction tests were compared: deionised water, 0.01 mol L⁻¹ CaCl₂, 1 mol L⁻¹ NH₄NO₃ and 0.005 mol L⁻¹ DTPA. The analytical data were coupled with measurement of the pH and Eh in extracts, mineralogical investigations and thermodynamic modelling using the PHREEQC-2 code. The changes in the pH of the equilibrated suspensions significantly influenced the metal extractabilities, with higher values in the lower pH regions. Although the DTPA procedure generally extracted the highest amounts of metals, it was found to be unsuitable for highly organic acidic forest soils, where anionic metal-DTPA complexes are assumed to be re-adsorbed on the positively charged surfaces of soil organic matter and oxides. The NH₄NO₃ extraction was also unsuitable due to the high ionic strength (1 mol L⁻¹), limiting the use of the thermodynamic speciation model and the formation of the Cu(NH₃)²⁺ complex, leading to acidification of the suspension. 0.01 mol L⁻¹ CaCl₂ can be proposed as the most appropriate extraction medium, suitable for speciation modelling and analytical determinations using ICP-techniques and having an ionic strength similar to that of the soil solution. The metals are present in free ionic forms or chlorocomplexes in the CaCl₂ extracts, preventing their re-adsorption on the positively charged surfaces of soil solids (organic matter, Fe- and Mn-oxides) in acidic and circum-neutral conditions.