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EurOCEAN 2000 - Vlaams Instituut voor de Zee

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The reaction of 6-mercaptopurine, leading to the fluorescent (6-mercaptopurine)2 is still in<br />

the stage of a badge process and we will concentrate here on the reaction of mercury with<br />

thiamine.<br />

A modified flow injection system was used for the <strong>de</strong>termination of mercury with thiamine. In<br />

the system, the highly fluorescent thiochrome was formed as a result of the redox interaction<br />

of Hg with thiamine.<br />

Thiochrome is retained on a solid support and its fluorescence is measured. Various resins have<br />

been tested and the highest fluorescence intensities were obtained when using Amberlite<br />

XAD-4. Moreover, different particle sizes of the packed resins were also investigated and<br />

particle diameters between 0.080-0.160 mm were selected for further experiments.<br />

Presently, the <strong>de</strong>tection limit for Pb is 3.6 ng mL -1 ; the repeatability is +/- 3% and the response<br />

time is 5 minutes.<br />

IRON, COBALT, MANGANESE AND COPPER<br />

The construction of the FI-CL system is outlined on the basis of the manifold for the<br />

<strong>de</strong>termination of dissolved Fe in seawater. For this purpose a FI-CL manifold based on the<br />

Fe(II) catalysed oxidation of luminol has been <strong>de</strong>veloped (Bowie et al.). In the manifold, three<br />

peristaltic pumps are used to <strong>de</strong>liver reagents, sample / buffer and wash solutions to the<br />

injection valve, preconcentration column and CL <strong>de</strong>tector. A six-port injection valve is used to<br />

transport the sample to the <strong>de</strong>tector. Three 3-way solenoid switching valves enable sample,<br />

sample plus standard addition(s) and wash solutions to pass sequentially through the manifold.<br />

In a first step, automation of the FI-CL system for the <strong>de</strong>termination of Fe was provi<strong>de</strong>d via a<br />

D/A <strong>de</strong>vice control interface card housed in a <strong>de</strong>sktop PC, previously used successfully inhouse<br />

for FI-CL systems. The <strong>de</strong>tection system currently consists of a quartz glass spiral flow<br />

cell mounted in front of an end-window photomultiplier tube, powered using a high voltage<br />

supply. CL signals are recor<strong>de</strong>d using a flat-bed chart recor<strong>de</strong>r or an integrator.<br />

FI-CL technologies for other trace elements (Co, Mn, Cu) are based on the above manifold<br />

with minor modifications to suit the specific CL reaction system. Instrumentation is generic to<br />

all systems.<br />

The automation of the FI-CL system for the <strong>de</strong>termination of Fe is achieved through a Labview<br />

(National Instruments) environment run on a laptop PC. A digital i/o, 24 line TTL PCMCIA<br />

card (DIO-24) enables full control of FI components (switching valve, injection valve, pumps,<br />

autosampler), using a transformer box to modify 5 V signals generated by the card. A<br />

multifunctional 16 analog input card is used for acquisition of CL signals generated from the<br />

miniature photon counting head of the PMT <strong>de</strong>tector. Signal output is modified through an inhouse<br />

interface board into a frequency that could be acquired by the DAQ-700 card. The<br />

chemiluminescence chemistries for the <strong>de</strong>termination of Fe, Co, Mn and Cu are summarized in<br />

table 2.<br />

685

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