The sequential injection system with adsorptive stripping voltammetric detection.

Two sequential injection systems have been developed for adsorptive stripping voltammetric measurement. One is for substances adsorbing at mercury, e.g. riboflavin. In this case, a simple arrangement with only sample aspiration is needed. Reproducibility was 3% and detection limit 0.07 muM. The measuring system was applied to determination of riboflavin in vitamin pills and to study the photodegradation process of riboflavin in aqueous solutions. In the second case, metal ions were determined. They have to be complexed before deposition on the mercury surface. Thus, both the sample and the ligand have to be aspirated in the system. In this case, the reproducibility was approximately 6% and the detection limit <0.1 ppm for cadmium, lead and copper when complexation with oxine was used. Dimethylglyoxime was used in determination of nickel and cobalt and nioxime complexes were used in determination of nickel and copper. With these complexing agents, the reproducibility was the same as with oxine, but the metals could be determined at concentrations lower than 0.01 ppm. Application of two ligands in a SIA system with AdSV detection was also studied. Simultaneous determination of copper, lead, cadmium and cobalt was possible by using oxine and dimethylglyoxime. Copper and nickel were simultaneously determined by using dimethylglyoxime and nioxime.

Interferences in a polypyrrole-based amperometric ammonia sensor.

The main focus of this article is on the interferences encountered when an amperometric ammonia sensor is used in matrices that are typical in clinical samples. The sensor is tested in presence of such interferences and ways to suppress them by sensor modification are presented. Two modification procedures are evaluated by comparing the stabilities, detection limits and signal-to-noise ratios of such sensors. Further, the issue of the ammonia-sensing mechanism of the polypyrrole electrode is addressed. Evidence is shown that a mobile counterion may be required for proper sensor operation. Such evidence supports the idea that polypyrrole undergoes a reversible redox reaction when ammonia is detected at submillimolar concentrations.

Application of sequential injection analysis to anodic stripping voltammetry.

Sequential injection analysis (SIA) technique has been applied to anodic stripping voltammetry (ASV). The sample and reagent volumes can easily be controlled by SIA. The technique also allows plating of the mercury film on-line and therefore substantially reduces generation of mercury containing waste. Repeated sample passage through the detector was used during the deposition step to enhance the sensitivity. The way solution handling is done in SIA allows an easy and effective medium exchange procedure increasing the selectivity of the method. This has been demonstrated by changing the stripping medium and having different complexing agents in the stripping solution. The observed potential shifts of the stripping peaks could theoretically be explained in the cases where the complexation constants are known. Calibration and the standard addition methods are discussed and demonstrated by determining copper in tap water as a method of testing the procedure.

Flow injection analysis with detection at mercury drop electrode in the presence of surfactants.

The surfactant presence in a sample may cause distortion of the flow injection peak obtained with amperometric detection at a mercury drop electrode. Distortion depends on detection parameters and flow system operating parameters and in some cases it may be eliminated by their careful optimization. Introduction of fumed silica into the carrier solution allows the dynamic removal of surfactant during the sample passage through the mixing coil. In the case of higher surfactant concentration in the sample, addition of fumed silica directly to the sample may be effective. Examples with amperometric detection as well as anodic stripping and adsorptive stripping voltammetric detection are described.

Anodic-stripping voltammetry of heavy metals in the presence of organic surfactants.

The efficacy of fumed silica for removal of sorption interferences by organic surfactants in the anodic-stripping voltammetry of heavy metals is demonstrated. Appropriate addition of silica to the sample solution rapidly "purifies" it from interfering surfactants during the nitrogen purge step. Up to at least 6 ppm of gelatin, Triton X-100, albumin or Liqui-Nox then does not affect the stripping response of cadmium, lead and zinc at the hanging mercury drop electrode. A relative standard deviation of 5.5% is obtained for 20 successive measurements of 1 x 10(-7)M lead in the presence of 2 ppm Triton X-100. Analogous improvements are observed at the mercury film electrode (in the presence of up to 60 ppm of these surfactants). The use of silica thus possesses the advantages of speed, efficiency, simplicity and low cost compared to other schemes for dealing with surfactant interferences in anodic-stripping voltammetry.

Algae columns with anodic stripping voltammetric detection.

The use of silica-immobilized algal cells for on-line column separation in conjunction with continuous monitoring of trace metals is described. Algae-silica preparations are highly suitable for flow analysis as they couple the unique reactivity patterns and high binding capacity of algal biomass with the hydrodynamic and mechanical features of porous silica. Such advantages are illustrated by using on-line anodic stripping voltammetry and the alga Chlorella pyrenidosa. Selective and exhaustive removal of interfering constituents circumvents common problems such as overlapping peaks and intermetallic effects. Effects of flow rate, pH, operation time, and other variables are reported. The system is characterized by high durability, simplicity, and economy and offers an attractive alternative to prevalent columns used for flow analysis.