Development of physico-chemical speciation procedures to investigate the toxicity of copper,lead, cadmium and zinc towards aquatic biota

A range of model compounds was studied to test the effect of complexing agents on the adsorption of copper, lead, cadmium and zinc by Chelex-100 resin, oxine porous glass, thiol porous glass and thiol resin, from seawater and distilled water. The thiol materials, while showing behaviour similar to Chelex-100 resin and oxine porous glass for zinc, cadmium and lead, retained copper much more strongly. Methods for measuring lipid-soluble metal complexes in waters were also studied. Bio-Rad SM2 resin was the most suitable extractant, although a citrate buffer of pH 5.7 was needed to prevent the co-adsorption of free metal ions. Seawater and various fresh waters were analyzed for trace metal speciation by using Chelex-100 resin, thiol resin and anodic stripping voltammetry to determine labile metal. Bio-Rad SM2 resin and hexane—butanol extraction were used for the estimation of lipid-soluble metal. The polluted water samples had higher fractions of labile and organic-soluble metal, but it was concluded that some of the waters contained unidentified ligands which caused speciation behaviour different from that of the synthetic solutions with model ligands. The factors involved in the choice of speciation procedures for the measurement of the toxic fraction of a metal in a water sample are discussed in detail.     

Separation of uranium from natural waters on chelex-100 resin

Uranium can be separated from fresh waters on Chelex-100 resin by careful control of the resin pH at 4.6 when sample solutions are adjusted to 3.9-4.7 after addition of 1,2-diaminocyclohexanetetraacetic acid. The interference of up to 500 mg of phosphate is avoided by addition of thorium(IV) at pH 3.9-4.0. After elution with 2 M nitric acid, uranium is determined spectrophotometrically with 4-(2-pyridylazo)resorcinol. Uranium can be concentrated from sea water at its natural pH without masking when the column is conditioned at pH 7.0 and a fluorimetric determination is used. The maximum recovery is 93% by spectrophotometry and 90% by fluorimetry. Interference by surfactants, sodium tripolyphosphate, NTA and EDTA at concentrations of 20 mg l^-1 reduces recoveries to 84–91%. Vanadium(V) interferes slightly in the spectrophotometric method.     

Preconcentration and determination of ultratraces of lead and bismuth

The recovery and preconcentration of Pb(II) and Bi(III) by coupling ion-exchange and precomplexation with 1,2-dihydroxy-3,5-benzenedisulphonic acid and 3,3',4'-trihydroxyfuchsone-2'-sulphonic acid has been investigated. Metal recoveries at 0.1-mg l . concentrations are better than 99% in the presence of cationic, anionic and non-ionic detergents, or an organic sequestering agent such as NTA, and at high ionic strength. Experiments with radiotracers show total recovery even at 15-ng l . concentrations. In the light of the results the procedure is proposed as a simple and rapid analytical method to preconcentrate Pb(II) and Bi(III).     

Development of column-pretreatment chelating resins for matrix elimination/multi-element determination by inductively coupled plasma-mass spectrometry

Chelating resins, two kinds of iminodiacetate derivatives (IDA) of cross-linked chitosan (CCS) were synthesized and investigated for adsorption capacity, matrix elimination and collection/concentration of analytes by a column pretreatment in a multi-element ICP-MS determination method. The adsorption behavior of 54 elements at the 10 ng ml(-1) level on chitosan derivatives in a packed mini-column was systematically examined. Almost 30 kinds of metal ions were recovered quantitatively at pH 5 with CCS-HP/IDA (cross-linked chitosan possessing N-2-hydroxypropyl iminodiacetic acid groups) column. Compared with available chitosan-iminodiacetate resin, CHITOPEARL CI-03, the recovery of the metal ions such as Cu, Pb and La is satisfactory with CCS-IDA (cross-linked chitosan possessing N,N-iminodiacetic acid groups) and CCS-HP/IDA using 2 M nitric acid as an eluent, which may be attributed to the difference of cross-linking and macroporous structure. Compared with Chelex-100, the adsorption efficiency is in the order: Chelex-100 > CCS-IDA > CCS-HP/IDA, especially in the chelating ability for alkaline earth metals. The resin with a longer spacer (CCS-HP/IDA) showed higher adsorption selectivity between heavy metal ions and alkaline earth metals at pH < 7. The separation efficiency of the major matrix cations in seawater (Na. K, Mg, Ca) has also been investigated, and matrix interference was negligible even in a seawater sample at pH 5 with CCS-HP/IDA. The recoveries of Mn at pH 5 with CCS-HP/IDA or Chelex-100 were almost 100%. However, those of Mg with each resin were 4 or 98%, respectively. The adsorption capacities of synthesized CCS-HP/IDA for Cu(II), Pb(II) and La(III) were 0.90, 0.65 and 0.34 mmol g(-1), respectively. Therefore, the chelating chitosan resins developed are applicable to the pretreatment of trace amounts of elements in various kinds of water samples.     

A flow system for the spectrophotometric determination of lead in different types of waters using ion-exchange for pre-concentration and elimination of interferences

A flow system for the spectrophotometric determination of lead in natural and waste waters is proposed. The determination is based on the colorimetric reaction between malachite green and iodide, followed by the formation of a ternary complex between those reagents and lead cations. The developed flow system includes a lead pre-concentration step in a column packed with a cationic resin (Chelex 100) operating in a sequential injection mode. To improve the mixture of sample and reagents, a flow injection approach was adopted for the colorimetric determination. This way a hybrid flow system, involving both sequential and flow injection concepts was designed. Another feature of the proposed system is the efficient elimination of major interferent species, such as cadmium and copper. The elimination of cadmium interference is obtained by complexing Cd²⁺ with chloride and retaining the formed negatively charged complexes in an anionic resin, AG1 X-8. As for copper, with the presence of both ionic resins as well as the conditions for cadmium elimination, it no longer acts as an interferent. Different ranges of lead concentration (50-300 and 300-1000 μg l⁻¹) can be determined with minor changes in the controlling software, useful for application to both natural and waste waters. Therefore, a detection limit of 25 μg l⁻¹ was achieved. Repeatability was evaluated from 10 consecutive determinations being the results better than 4%. The recoveries of lead spikes added to the samples ranged from 93 to 102%. The sampling frequency was 17 and 24 determinations per hour, for 50-300 and 300-1000 μg l⁻¹ ranges, respectively.     

Stability of manganese dioxide by guar gum in the absence or presence of surfactants

Stability of the manganese dioxide (MnO₂) suspensions by non-ionic guar gum (GG) in the absence or presence of the surfactants: anionic sodium dodecyl sulphate (SDS), cationic hexadecyltrimethylammonium bromide (CTAB) and non-ionic Triton X-100 (t-octylphenoxypolyethoxyethanol) and their equimolar mixtures (SDS/TX-100; CTAB/TX-100) was measured using turbidity. The obtained results of the manganese dioxide suspensions stability were discussed together with the adsorption data and with the data concerning the thicknesses of the adsorption layers. In order to gain more information about the structure of the electric double layer surface charge density and the zeta potential measurements were performed. The obtained results show that the addition of guar gum to the MnO₂ suspensions increases MnO₂ stability. The larger this increase is, the higher is the concentration of the polymer (concentration range 10–200 ppm). Moreover, the addition of single surfactants also causes the increase in the effectiveness of stabilizing the manganese dioxide suspensions. The reason for that is formation of multilayer complexes between the polymer and the surfactants. In such a system both the adsorption of polymer and the thickness of polymer adsorption layer increase. The greatest increase in the stability of MnO₂/GG suspensions was provided by the mixture of anionic and non-ionic surfactants due to a strong synergistic effect. Also, mixing the polymer and two surfactants reduces the stability of the suspension.     

Terpyridine-based smart organic-inorganic hybrid gel as potential dye-adsorbing agent for water purification

A terpyridine-based organic-inorganic hybrid gelator possessing triethoxylsilane moiety was synthesized and its adsorption capacity for aromatic dyes in the absence and the presence of metal ions such as Zn²⁺ and Cu²⁺ was measured by UV-vis spectroscopy. From aqueous solutions of dyes, the hybrid gel, in the absence of metal ions, adsorbed 97.4% for basic blue 41, 94.2% for crystal violet, and 41.5% for bromocresol green. When metal ion was present, the adsorption capacity of dried hybrid gel 1 for the anionic dye bromocresol green significantly increased due to the enhanced electrostatic interaction between cationic gel and anionic dye. Thus, this hybrid gel can efficiently adsorb various toxic dyes in water.     

Influence of surfactants on the adsorption and elektrokinetic properties of the system: guar gum/manganese dioxide

The adsorption of non-ionic polysaccharide—guar gum (GG) in the presence or absence of the surfactants: anionic SDS, cationic CTAB, nonionic TX-100 and their equimolar mixtures SDS/TX-100, CTAB/TX-100 from the electrolyte solutions (NaCl, CaCl₂) on the manganese dioxide surface (MnO₂) was studied. The increase of GG adsorption amount in the presence of surfactants was observed in every measured system. This increase results from formation of complexes between the GG and the surfactant molecules. This observation was confirmed by the determination of the influence of GG on surfactants adsorption on the MnO₂ surface. The increase of GG adsorption on MnO₂ was the largest in the presence of the surfactant mixtures (CTAB/TX-100; SDS/TX-100) which is the evidence of the synergetic effect. The smallest amounts of adsorption were obtained in the presence of TX-100, which results from non-ionic character of this surface active agent. In the case of single surfactant solution CTAB has the best efficiency in increasing the amount of GG adsorption on MnO₂ which results from strong interactions with GG and also with the negatively charged surface of the adsorbent. In order to determine the electrokinetic properties of the system, the surface charge density of MnO₂ and the zeta potential measurements were performed in the presence of the GG macromolecules and the above mentioned surfactants and their mixtures. The obtained data showed that the adsorption of GG or GG/surfactants complexes on the manganese dioxide surface strongly influences the diffused part of the electrical double layer (EDL)—MnO₂/electrolyte solution, but has no influence on the compact part of the electric double layer. This is the evidence that the polymers chains are directly bonded with the surface of the solid and the surfactants molecules are present in the upper part of the EDL.     

Determination of zinc in foods by fluorescence spectroscopy in micellar media

The effect of cationic [cetyltrimethylammonium bromide (CTAB), Zephiramine], non-ionic (Triton X-100, Brij-35) and anionic (sodium lauryl sulphate) surfactant micelles on the fluorescence intensity of the zinc 5,7-dichloro-2-methylquinolin-8-ol chelate is described. In Brij-35 or CTAB micellar media, the fluorescence is about 25 times greater than that obtained in ethanol-water. The relationship between fluorescence intensity and experimental variables was studied in order to develop a procedure for the fluorimetric determination of zinc. Linear calibration graphs were obtained in the ranges 3–100 and 50–400 ng Zn ml^?1. The detection limit is 3 ng ml^?1. The method was successfully applied to the determination of zinc in food samples and drinking waters.     

The effect of surfactants on the pH transition interval of bromothymol blue immobilized on XAD 4

Cationic, anionic and non-ionic surfactants adsorb readily from aqueous solution on to Amberlite XAD 4. The ionic surfactants cause the pH of the solution in contact with the resin to differ from that in the bulk of solution, cationic surfactants increasing the interfacial pH and anionic surfactants decreasing it. This causes a shift in the pH transition interval of a co-adsorbed pH indicator when measured with respect to the bulk solution. The quantity of ionic surfactant adsorbed tends to a constant value (presumably monolayer coverage) with increasing solution concentration, this amount being a function of the individual surfactant, whereas non-ionic surfactants readily form multilayers. Significant adsorption occurs when the surfactant possesses at least 14 carbon atoms.     

Indirect determination of surfactants by adsorptive stripping voltammetry

The effect of some anionic, cationic and nonionic surface-active substances on the suppression of adsorptive accumulation of the bis(dimethylglyoximato)nickel(II) complex, Ni(DMG)₂, is described. Competitive adsorption of surfactants can be used to determine surfactants commonly used in commercial detergents. Triton X-100 shows the most pronounced effect on the peak height. The shape of the calibration curve depends on the concentration and on the adsorption potential. Highest sensitivity is obtained when equilibrium between Ni(DMG)² in solution and on the electrode surface is attained rapidly. Under these conditins, the detection limit is 1 μ 1^?1 Triton X-100. Calibrations are linear over 1–2 orders of magnitude.     

Electrokinetic potential of bentonite and kaolin particles in the presence of polymer mixtures

In order to elucidate the mechanisms of flocculation by polymer mixtures, the effect of adsorption of non-ionic poly(ethylene oxide) — PEO, two samples of strongly (SNF FO 4800) and medium charged (SNF FO 4350) cationic and two samples of medium (SNF AN 935) and weakly charged (SNF AN 905) anionic polyelectrolytes (PE) as well as their binary mixtures on the electrokinetic potential of bentonite and kaolin particles has been studied. It is shown that in the presence of PEO-anionic/cationic polymer mixture, the electrokinetic potential of particles is determined by the adsorption of the polyelectrolyte; neither cationic nor anionic segments can be displaced by the non-ionic polymer. In mixtures of cationic and anionic polyelectrolytes, the ζ-potential of particles is determined by the adsorbed amount of anionic polymer independently of the charge density of PE and way of addition of the mixture components to the suspension, i.e. (1) first adding the cationic polymer, then the anionic one, or (2) first adding the anionic polymer then the cationic one, or (3) adding an increasing amount of pre-prepared 1: 1 mixture. The highest absolute ζ-potential values are observed for pH 7.5 when the surface of bentonite or kaolin particles is “purely” negatively charged and the anionic PE layer is most extended because of few contacts to the surface. With decreasing the pH, the (negative) ζ-potential of particles decreases due to appearance of a small amount of positive charges on the surface that bond an increasing amount of negative segments and results in shrinking of the adsorbed layer of the anionic PE. It is shown also that the electrokinetic potential of particles in anionic and cationic PE mixtures at all studied pH (4, 5, and 7.5) depends on the spatial distribution of negatively charged segments near the surface. The regularities observed are explained by formation of long loops and tails of anionic segments on the surface because of the small number of contacts to the surface; the cationic polyelectrolyte forms on the surface a thin layer with a big number of contacts and which is hidden behind the more extended anionic polymer layer.     

阴阳离子表面活性剂混合体系在克拉玛依油田中获得超低界面张力

利用阴阳离子表面活性剂复配技术,在克拉玛依油田实际油水体系中获得了超低界面张力.通过添加非离子保护剂的第三组分,阴阳离子表面活性剂混合体系在克拉玛依油田回注水体系中的溶解度大大提高.确定了相关体系能够获得超低界面张力的表面活性剂的浓度和混合的比例范围,在克拉玛依油田的多个实际油水体系中获得了具有较大复配比例和较低表面活性剂浓度的实际配方,其中部分体系油水界面张力可接近10-4mN·m-1.同时,这类阴阳离子表面活性剂混合体系具有很好的抗吸附能力,在石英砂吸附72 h后体系依然呈现优良的超低界面张力.     

Speciation of copper in fresh waters

The cations and readily dissociable complexes of copper are separated from copper adsorbed on inorganic and organic particulate species in river and pond waters by selective sorption on a strong-acid cation-exchange resin, AG 50W-X12, and a chelating resin, Chelex-100, for atomic absorption spectrometry. The sorption behaviour after the pH change and removal of carbon dioxide suggests that the dominant low-molecular-weight copper species in river waters are neutral CuCO⁰₃ and Cu²⁺ ions.     

A review on experimental studies of surfactant adsorption at the hydrophilic solid-water interface

The progresses of understanding of the surfactant adsorption at the hydrophilic solid-liquid interface from extensive experimental studies are reviewed here. In this respect the kinetic and equilibrium studies involves anionic, cationic, non-ionic and mixed surfactants at the solid surface from the solution. Kinetics and equilibrium adsorption of surfactants at the solid-liquid interface depend on the nature of surfactants and the nature of the solid surface. Studies have been reported on adsorption kinetics at the solid-liquid interface primarily on the adsorption of non-ionic surfactant on silica and limited studies on cationic surfactant on silica and anionic surfactant on cotton and cellulose. The typical isotherm of surfactants in general, can be subdivided into four regions. Four-regime isotherm was mainly observed for adsorption of ionic surfactant on oppositely charged solid surface and adsorption of non-ionic surfactant on silica surface. Region IV of the adsorption isotherm is commonly a plateau region above the CMC, it may also show a maximum above the CMC. Isotherms of four different regions are discussed in detail. Influences of different parameters such as molecular structure, temperature, salt concentration that are very important in surfactant adsorption are reviewed here. Atomic force microscopy study of different surfactants show the self-assembly and mechanism of adsorption at the solid-liquid interface. Adsorption behaviour and mechanism of different mixed surfactant systems such as anionic-cationic, anionic-non-ionic and cationic-non-ionic are reviewed. Mixture of surface-active materials can show synergistic interactions, which can be manifested as enhanced surface activity, spreading, foaming, detergency and many other phenomena.     

Differential-pulse polarographic determination of selenium species in contaminated waters

Selenium(IV), in the concentration range 2–100 μg l^?1 in contaminated waters, is determined by using the sensitive adsorption-controlled peak obtained by differential pulse polarography in dilute acid solution. Interfering heavy metals are removed on Chelex-100 resin. Selenium(VI) is not electroactive but can be determined after photolytic reduction in the absence of oxygen. Anion-exchange preconcentration is necessary if the total selenium is below the detection limit of 2 μg l^?1.     

Use of the diffusion gradient thin film method to measure trace metals in fresh waters at low ionic strength

The diffusion gradients in thin films (DGT) method was investigated and used to measure trace metal concentrations in river water. The principle of DGT is that trace metal ions diffuse through a thin polyacrylamide gel film (the diffusion gel layer) and are subsequently immobilised and concentrated on a layer of Chelex-100 resin embedded in another polyacrylamide gel film (the resin gel layer). These layers are mounted in a plastic holder, which exposes a fixed area of the diffusion gel layer to the water being monitored. Replacement of the normal agarose cross-linked diffusion gel with bisacrylamide cross-linked gel altered the ion uptake properties of DGT. The bisacrylamide cross-linked gel weakly, and with little selectivity, bound metal ions prior to their irreversible binding to Chelex-100. Trace metal ion uptake by these DGT devices was thus dependent on ionic strength and temperature, although the ionic strength effect is relatively small for most natural waters and negligible in sea water. The concentrations of Cd, Co, Cu, Ni, Pb, and Zn in the Water of Leith, an urban stream in Dunedin, New Zealand, were measured by DGT and the results compared with total dissolved concentrations of these metals measured in conventional (bottle) samples collected in parallel with the DGT monitoring. Greater than 90% of the total dissolved Cd and Zn; 20-40% of the total dissolved Co, Ni, and Pb; and 5% of the total dissolved Cu was available to the DGT method.     

Preconcentration of inorganic mercury with an anion-exchange resin and direct reduction—aeration measurements by cold-vapour atomic absorption spectrometry

Inorganic mercury ions (5–50 ng l^-1) present in natural waters (500 ml) are concentrated on anion-exchange resin (0.2 g; chloride form) in a batchwise operation. The resin is filtered off and introduced into a bubbler containing tin(II) solution. The adsorbed mercury ions are reduced to the metal and vaporized with a stream of air in a closed system. Satisfactory recoveries are obtained for sea waters made 0.1 M in nitric acid, and for river and spring waters also made 0.1 M in nitric acid or 0.01 M in ammonium thiocyanate. The method preconcentrates traces of inorganic mercury ions by an order of magnitude, and is also effective in preventing mercury loss during sample storage.     

The Spectrophotometric Determination of gallium (III) Using O-Hydroxyhydroquinonephathalein in the Presence of Surfactant Micellar

Abstract

The color reaction systems between various metal ions and o-hydroxyhydroquinonephthalein(Qnph) as a xanthene dye, in the presence of various water soluble surfactants(cationic. anionic, non-ionic surfactants) alone or in combination, were systematically investigated at various pH areas. The coexistence of cationic and non-ionic surfactants, such as Zephiramine (Zp) and Brij 35, was most effective for the color reaction systems between Qnph and gallium(III), as a metal ion, at weakly acidic media. By using the color reaction between Qnph and gallium(III) in the coexistence of Zp and Brij 35, an improved and sensitive spectrophotometric determination of gallium(III) was proposed as method 1, and the calibration curve was rectilinear in the range of 0～7.0 μg of gallium(III) in a final solution of 10ml at pH 6.4. The apparent molar absorptivity was 1.5 × 10⁵ 1 mol^?1 cm^?1 at 560 nm, and the interference of foreign ions was decreased by ½～ ¼-fold in comparison with other methods; method 3—in the presence of Zp alone at pH 6.4, method 2—in the presence of Tween or Brij 35 alone, without Zp, at pH 8. Thus, the use of Qnph as a xanthene dye and the combination of cationic and non-ionic surfactants, such as Zp and Brij 35(perhaps, on the mixed micellar media), was most effective and its color reaction was used for the separative assay of gallium(III).