Preconcentration anions

The capacity to preconcentrate anions has enabled the use of chitosan and its derivatives in modified electrodes, for application in sensor and biosensor electrochemistry [233]. To facilitate improving water solubility of biologically useful chitosan derivatives, N-methylene phosphonic chitosan has been prepared using a one-step reaction that allowed homogeneous modifications [234]. 

Ion Removal and Metal Oxide Electrodes. The ethylenediamine ( )-functional silane, shown in Table 3 (No. 5), has been studied extensively as a sdylating agent on siUca gel to preconcentrate polyvalent anions and cations from dilute aqueous solutions (26,27). Numerous other chelate-functional silanes have been immobilized on siUca gel, controUed-pore glass, and fiber glass for removal of metal ions from solution (28,29). 

Last time development of methods of iodine determination, which include preliminary sorption preconcentration of microcomponents and their subsequent determination in phase of concentrate get great practical significance. Silica gel (SG) with adsorptively modified quaternary ammonium salts (QAS) gets properties of anion-exchange resin. The sorbents modified in this way can be used successfully for determination of different anions. 

In this work hybrid method is suggested to determine anionic surfactants in waters. It is based on preconcentration of anionic surfactants as their ion associates with cationic dyes on the membrane filter and measurement of colour intensity by solid-phase spectrophotometry method. Effect of different basic dyes, nature and hydrophobicity of anionic surfactants, size of membrane filter pores, filtration rate on sensitivity of their determination was studied. Various cationic dyes, such as Methylene Blue, Crystal Violet, Malachite Green, Rhodamine 6G, Safranin T, Acridine Yellow were used as counter ions. The difference in reflection between the blank and the sample was significant when Crystal Violet or Rhodamine 6G or Acridine Yellow were used. 

The aqueous micellai solutions of some surfactants exhibit the cloud point, or turbidity, phenomenon when the solution is heated or cooled above or below a certain temperature. Then the phase sepai ation into two isotropic liquid phases occurs a concentrated phase containing most of the surfactant and an aqueous phase containing a surfactant concentration close to the critical micellar concentration. The anionic surfactant solutions show this phenomenon in acid media without any temperature modifications. The aim of the present work is to explore the analytical possibilities of acid-induced cloud point extraction in the extraction and preconcentration of polycyclic ai omatic hydrocai bons (PAHs) from water solutions. The combination of extraction, preconcentration and luminescence detection of PAHs in one step under their trace determination in objects mentioned allows to exclude the use of lai ge volumes of expensive, high-purity and toxic organic solvents and replace the known time and solvent consuming procedures by more simple and convenient methods. 

Sodium dodecylsulphate was selected as an anionic surfactant Factors affecting acid-induced cloud point extraction including surfactant, hydrochloric acid, PAHs, and electrolyte concentration, centrifugation have been examined. Finally, we applied the optimized acid-induced CPE system for combination of the extraction and preconcentration steps with fluorimetric determination of some representatives of PAHs. Suggested means was used for PAHs determination in tap water. 

Table 2.6. Anion preconcentration (from author s own files)...

Anion Preconcentration method Analytical finish Detection limit (pg/1) Section Reference... 

Methods of improving the detection limits for anions by preconcentration are reviewed in Table 2.6. 

Falkner and Edmond [334] determined gold at femtomolar quantities in seawater by flow injection inductively coupled plasma quadrupole mass spectrometry. The technique involves preconcentration by anion exchange of gold as a cyanide complex, [AulCNjj], using 195Au radiotracer (ti/2 = 183 days) to monitor recoveries. Samples are then introduced by flow injection into an inductively coupled plasma quadrupole mass spectrometer for analysis. The method has a detection limit of 10 fM for 4 litres of seawater preconcentrated to 1 ml, and a relative precision of 15% at the 100 fM level. 

Chen et al. [31] preconcentrated "technetium in seawater on an anion exchange column to determination in amounts down to 3mBq/m3. 

The copper flow-through CL sensor comprised an anion-exchange column having luminol and cyanide coimmobilized on the resin, while copper was temporarily retained by electrochemical preconcentration on a Au electrode placed in an anodic stripping voltammetric cell [64], Injection of 0.1 mol/L NaOH through the column eluted the reagents, which then reacted with copper, stripped from the electrode to produce a CL signal. The response was linear in the 0.01-10-pg/L... 

In one study, however, atmospheric pressure chemical ionisation (APCI)-MS was applied for the simultaneous determination of LAS and octylphenol ethoxylates (OPEO) in surface waters after preconcentration by solid-phase extraction (SPE) on Cis cartridges [1]. In the chromatogram from a Ci-reversed phase (RP) column, peaks arising from both the anionic LAS and the non-ionic OPEO were detected after positive ionisation, while in negative ionisation mode, OPEO were discriminated and only the anionic surfactant was observed. Surprisingly, the relative sensitivity for detection of LAS was approximately five times higher in positive ion mode, which led the authors to the conclusion that this ionisation mode was desirable for quantitative work. 

With the aim of minimising the time taken in the preconcentration, and extending the chemical analysis of surfactants to more complex aqueous matrices in which very low detection limits are required, preconcentration techniques using solid-liquid extraction with various adsorbent materials, such as XAD [27] and anionic exchange resin [28] have been developed. 

The major anions and cations in seawater have a significant influence on most analytical protocols used to determine trace metals at low concentrations, so production of reference materials in seawater is absolutely essential. The major ions interfere strongly with metal analysis using graphite furnace atomic absorption spectroscopy (GFAAS) and inductively coupled plasma mass spectroscopy (ICP-MS) and must be eliminated. Consequently, preconcentration techniques used to lower detection limits must also exclude these elements. Techniques based on solvent extraction of hydrophobic chelates and column preconcentration using Chelex 100 achieve these objectives and have been widely used with GFAAS. 

In 1985, Ruzicka and Hansen established the principles behind flow injection optosensing [13-15], which has subsequently been used for making reaction-rate measurements [16], pH measurements by means of immobilized indicators [17,18], enzyme assays [19], solid-phase analyte preconcentration by sorbent extraction [20] and even anion determinations by catalysed reduction of a solid phase [21] —all these applications are discussed in Chapters 3 and 4. Incorporation of a gas-diffusion membrane in this type of sensor results in substantially improved sensitivity (through preconcentration) and selectivity (through removal of non-volatile interferents). The first model sensor of this type was developed for the determination of ammonium [13] and later refined by Hansen et al. [22,23] for successful application to clinical samples. 

This technique of MEUF has also been successfully employed for the recovery of thuringiensin [258], removal of cresols [262], extraction of chromate anion [257], removal of dissolved organic pollutants [256], removal of -alcohols [263],preconcentration and removal of iron [260], and preconcentration of aniline derivatives [261].Kandori and Schechter [264] have given a detailed account of selecting surfactants for MEUF. The design characteristics of micellar enhanced utrafilters and cross-flow ultrafiltration of micellar surfactant solutions have been described by Markets et al. [265]. 

An agarose-based anion exchanger loaded with chromotropic acid was employed for Cu preconcentration. Five variables were studied simultaneously by the experimental design... 

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