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Proceedings of the International Cyanide Detection Testing Workshop

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Polymeric membrane based ion selective electrodes (ISE)<br />

The American Society <strong>of</strong> <strong>Testing</strong> and Materials (ASTM) ISE method is <strong>the</strong> only approach<br />

that has been widely used to detect cyanide exposure in marine fi shes. The method involves<br />

an acid digestion <strong>of</strong> <strong>the</strong> fi sh to liberate hydrogen cyanide gas, and capture <strong>of</strong> cyanide ions in<br />

sodium hydroxide solution after refl ux distillation. Chemicals must be added to help remove<br />

interfering substances such as chlorine and hydrogen sulfi de. An ISE meter manufactured<br />

by Thermo-Orion, using a membrane made <strong>of</strong> Agl or Ag 2 S, is <strong>the</strong>n used to analyze cyanide<br />

concentrations, based on its interaction with silver. ISE methods may also work for <strong>the</strong><br />

detection <strong>of</strong> thiocyanate.<br />

Spectrophotometric and fl uorescence methods<br />

Both spectrophotometric and fl uorescence methods require extraction techniques to isolate<br />

cyanide and eliminate interferences from blood. Spectrophotometric methods have been<br />

used for detection <strong>of</strong> cyanide, thiocyanate and ACTA. One common approach involves<br />

<strong>the</strong> König dye syn<strong>the</strong>sis to form a cyanide halide that is reacted with an aromatic amine to<br />

produce a glutaconic aldehyde product that is measured in <strong>the</strong> visible region <strong>of</strong> <strong>the</strong> spectrum.<br />

Spectrophotometric methods have adequate sensitivity, but <strong>the</strong>y may lack specifi city due to<br />

interferences from o<strong>the</strong>r chemical species commonly present during <strong>the</strong> analysis <strong>of</strong> cyanide,<br />

especially thiocyanate and thiosulfate. They also require lengthy preparation times and <strong>the</strong><br />

products may be unstable. A number <strong>of</strong> fl uorometric assays are available to determine<br />

cyanide, which have several advantages over spectrophotometric methods, including a lack <strong>of</strong><br />

interference from thiosulfate and greater sensitivity.<br />

Flow injection analysis (FIA)<br />

The FIA method is a simple one with high reproducibility. The approach involves injecting<br />

a sample solution containing <strong>the</strong> target molecule into a fl ow tube where it reacts with certain<br />

chemicals. When <strong>the</strong> products reach <strong>the</strong> detector, <strong>the</strong> target molecules in <strong>the</strong> sample are<br />

measured. The user is able to control <strong>the</strong> measuring conditions precisely and also has <strong>the</strong><br />

capability to continuously measure cyanide.<br />

Biosensors for detecting cyanide ion<br />

These methods primarily evaluate chemical reaction products based on <strong>the</strong> enzyme inhibition<br />

<strong>of</strong> cyanide, cyanide degrading enzymes, and microbial sensors which measure oxygen uptake<br />

by bacteria, yeast or o<strong>the</strong>r microorganisms. Biosensors have a rapid response, high selectivity,<br />

and a pollution free procedure. Most biosensors have <strong>the</strong> advantages <strong>of</strong> being portable, low<br />

cost, easy to use, and high selectivity. These methods, however, rely on chemical and physical<br />

procedures that can be slow, complex, and require <strong>the</strong> use <strong>of</strong> expensive equipment and<br />

environmental loading reagents. O<strong>the</strong>r limitations <strong>of</strong> biosensors include degradation <strong>of</strong> <strong>the</strong><br />

biological components that make up <strong>the</strong>se sensors, inconsistent electrochemical signals, and<br />

diffi culty producing suffi cient quantities and activities <strong>of</strong> enzymes or microbes on which <strong>the</strong>se<br />

sensors depend.<br />

Recently, one group applied a biosensor approach to marine fi shes. Organs <strong>of</strong> <strong>the</strong> fi sh were<br />

homogenized with NaOH and a fungal enzyme extract was used to produce formate from<br />

metal-cyanide complexes; <strong>the</strong> formate was converted using an enzyme to NADH which was<br />

17

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