679

Review

Amalgam Electrodes for Electroanalysis

yvind Mikkelsen, Knut H. Schrder*
Norwegian University of Science and Technology, Department of Chemistry, N-7491 Trondheim, Norway * e-mail: Knut.Schroder@chem.ntnu.no; Oyvind.Mikkelsen@chem.ntnu.no Received: September 27, 2002 Final version: November 11, 2002 Abstract Liquid mercury is a unique material for the indicator electrode in voltammetry. One reason for this is the high overvoltage for hydrogen formation, thus extending the actual potential window. Diluted amalgams are important reaction products in voltammetric (polarographic) processes, however liquid amalgams are rarely used directly as electrode material for analytical purposes. Because of the fact that voltammetry is very suitable for field and remote monitoring, issues concerning the use of mercury electrodes in environmental analyses have led to considerable research effort aimed at finding alternative tools with acceptable performance. Solid electrodes are such alternatives. Different types of electrodes are reviewed. In particular, solid amalgam electrodes are very promising, with acceptable low toxicity to be used for field measurements. Solid amalgam electrodes are easy and cheap to construct and are stable over a reasonable time up to several weeks. Assessment of the toxicity risk and the long time stability for remote and unattended monitoring is discussed. The differences between solid dental amalgam electrodes, made by using techniques known from dental clinical practice, and mercury film or mercury layer electrodes on solid substrates are reviewed. In particular the dental technique for constructing solid amalgam electrodes gives advantage because its fast and inexpensive. Also the technique for making dental amalgam has been explored and optimized over years by dentists, giving advantage when the same technique is used for constructing electrodes. Dental amalgam electrodes has been found to act similar to a silver electrodes, but with high overvoltage towards hydrogen. This make it possible to use the dental amalgam electrode for detection of zinc, cobalt and nickel in additions to other metals like lead, copper, thallium, cadmium, bismuth, iron etc. Also the use for reducible organic compounds is expected to be promising. Keywords: Voltammetry, Polarography, Stripping, Dental, Amalgam, Electrode, Mercury, Heavy metals, Medium exchange

1. Introduction
Voltammetry is known as a very useful method, not only for more fundamental studies of electrode reactions, but also for applied analytical purposes. Important examples of applications are in the field of environmental pollution monitoring and to control industrial products and effluents. The popularity of this technique has varied very much over time since Professor Jaroslav Heyrovsky invented the polarographic method, which dates from 1922. This is on one side due to the increasing number of alternative methods, but also on the other side the stepwise improvement in electronics and instrumentation. The concern of pollution and pollution control during the last decades has also been important in this regard. On the other hand, and as will be discussed later, the uniqueness of using the toxic liquid mercury as electrode material is a serious limitation. Discussions about the extent of the health risk of using mercury for voltammetric purposes take place. However, for off-laboratory measurements this cannot be accepted, at least of psychological and political reasons.

1.1. Advantages Using Voltammetric Analyses During the last years many new analytical methods have been developed [1]. Regarding this, the present and future role of voltammetry has to be considered. In a wellequipped laboratory with a great number of samples to be analyzed, normally other methods will be preferred. However, there are reasons to use voltammetry, even in a laboratory: The method is easy to use for many actual measurements, in particular for compounds of environmental interest. In contrast to most other methods, chemical speciation and not only the total amount can be measured. Finally, if it is needed to use mercury, the health risk will be negligible using controlled laboratory routines [2]. However, the psychological and political reason not to use mercury should not be underestimated. The main interest for voltammetry is when no other analytical methods are applicable. Continuous and remote measurements and monitoring in the field are typical tasks where very few or no other methods are appropriate at low concentration levels. For such purposes, classical analytical techniques are not sufficiently sensitive, and upcountry to locate huge instruments with the required infrastructure and at several locations is very inconvenient, and normally this is not possible at all.

Electroanalysis 2003, 15, No. 8

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1040-0397/03/0805-0679 $ 17.50+.50/0

680

. Mikkelsen, K. H. Schrder

2. Liquid Electrodes
The advantages of using liquid electrodes in voltammetry are obvious. A new and reproducible surface is easily formed without any interference from previous measurements or from contaminants, and cleaning or refreshing procedures are not required. On the other hand, handling of drop systems is technically somewhat more complicated than using solid electrodes.

amalgam electrodes. The use of dilute amalgams and amalgam films [4, 5] electrodes, or a mercury meniscus on silver electrode may reduce the amount of used mercury greatly. However, even for these electrodes the risk due to the toxicity of mercury in off-laboratory handling is not eliminated.

3. Solid Electrodes
A serious limitation in analytical voltammetry is the reduction of hydrogen at the indicator electrode with the formation of hydrogen gas. This narrows the measurement window at negative potentials, making determination of zinc and several other species impossible, due to the current from the formation of hydrogen gas. For a platinum electrode, used in an acid solution, the actual potential range is in the region 1 to 0.3 V (vs. SCE) [6]. Oxidation of the electrode material, the matrix to be investigated or the formation of oxygen gas limits the measurement window at positive potentials, correspondingly. However, the latter limitation is normally less important because most of actual measurements, like most heavy metals etc., happen to take place in the negative potential region. An overview of potential ranges for some solid electrodes used in voltammetry is given by Wang [7].

2.1. Liquid Mercury Electrodes During the history of polarography, the use of other electrode materials than liquid mercury is very unusual. This is due to the unique properties of mercury, with high overvoltage for hydrogen evolution reaction. This will extend the measuring window, enabling one to measure compounds appearing in the more negative potential range, like zinc. On the other hand, due to the oxidation of mercury, such electrodes cannot be used at more positive potentials. Another advantage using mercury is that diluted, liquid amalgams are formed with many metals during the reduction process. This is important in stripping techniques and contributes to better-defined voltammetric curves. The third advantage appears due to the liquid state, as pointed out above.

3.1. Mercury-on-Solid-Substrate Electrodes 2.2. Liquid Amalgam Electrodes The word amalgam has different meanings in different contexts and in different languages, from the more general term united into one body to the more specific term alloy of mercury and one or more metals. The latter definition is used in voltammetry. The direct use of liquid, i.e., diluted, amalgam electrodes in analytical voltammetry is very limited, and is mainly used to investigate electrode processes [3]. However, such electrodes are frequently being formed starting from pure mercury during the reduction process. Due to the high extent of dilution, this liquid amalgam possesses almost the same mechanical properties and toxicity as liquid mercury itself. This is of importance from an analytical point of view being the second step in voltammetric and potentiometric stripping techniques when the diluted amalgam is reoxidized to mercury and metal ions. In 1947 Airey [6] observed that the actual most negative potential range for the above mentioned platinum electrode, as well as with a silver electrode, was extended from 0.3 V to 2.1 V by amalgamation with mercury. It is stated in that article that the best results are obtained with the platinum electrode. The amalgamation of platinum will make a very thin film of Pt/Hg only [8], thus frequently repeated preparations will be needed. Below it is differed between electrolytically deposited mercury film and film formed by dipping into liquid mercury. Obviously, this gives very little, if any, differences because a sufficiently thin film is not strictly a solid or a liquid. 3.1.1. Electrolytically Deposited Mercury Film Electrodes A great number of substrates have been used for mercury deposition. This includes the following examples: Silver [9], platinum [10, 11], iridium [12, 13], gold [14] and carbon in different forms [15]. Extensive work for in situ measurements has been performed by Luther III and co-workers [16 23], using solid gold microelectrodes plated with mercury. Another interesting approach for in situ studies is worked out by Buffle and his group [24 31]. They use a micro array system, with an iridium matrix plated with mercury. To increase measuring stability by avoiding electrode fouling they protect the electrode using an agarose gel membrane. This acts as a dialysis membrane by allowing

2.3. Liquid Mercury and Amalgams: Toxicological Consequences There has, been a growing concern about the general use of mercury, due to its toxicity. This includes the use of pure mercury as an electrode material in voltammetry. Even for laboratory use, restrictions are expected to appear in the future. Therefore it is of great interest to find alternative electrode materials to the liquid mercury and the liquid
Electroanalysis 2003, 15, No. 8

Amalgam Electrodes

681

the diffusion of metal ions and complexes and by hindering the diffusion of colloids and macromolecules. However, a problem with deposition of mercury onto metal substrates is the stability over time, due to partly formations of amalgams [32]. Several methods are worked out for analyses of heavy metals, also applicable for seawater, one example is [33]. The use of microelectrode arrays with mercury deposit on carbon fibers is an interesting approach for increased sensitivity of stripping analyses [34]. Mercury salts can also be mixed with the electrode material to generate a mercury film [35]. Finally, amalgam formation can be used for chemical speciation studies [36, 37]. 3.1.2. Electrodes Prepared by Dipping into Liquid Mercury An alternative to electrochemical plating of mercury onto metal substrate electrode is simply to dip the electrode and co-workers directly in mercury as suggested by Novotny [38 46], that have further developed such electrode systems, initially proposed by Airey [6]. In their first versions [38], the electrodes were designed as given in Figure 1, by using a glass capillary of about 5 mm outer diameter and 1 mm inner diameter. After insertion of a silver wire of a diameter of about 0.5 mm into the capillary, the glass was conically narrowed and the space between the silver wire and the glass was tightened with an acrylic resin. After hardening of the resin, the metallic cross-section of the capillary was polished and dipped into a beaker with liquid mercury, kept under water. Subsequently, the excess of mercury sticking to the silver disk was gently knocked off. The electrode was activated by cyclic polarizations before each major series of experiments. In the later versions [44], in some extent the design of the electrode was modified, as shown in Figure 2. Silver or copper powder was packed into a glass capillary with an inner diameter of about 0.5 mm; electric contact was made with a platinum wire inserted into the powder. The metal powder was then amalgamated by dipping the unit into liquid mercury. The resulting solid amalgam disk was polished and covered by a mercury meniscus by a new dipping into a small volume of liquid mercury for 10 20 s. Then the electrode was electrochemically activated and further treated as above. Voltammetric analyses using such electrodes are convenient, as very little liquid mercury is required. As expected, they behave analytically very similar to mercury electrodes, as mercury is the active part, being in contact with the actual solution. It is of interest to compare the earlier versions of the electrode [38] with the later version [44]. In the earlier versions, silver and copper are used as a substrate for liquid mercury, by dipping the metal electrode into mercury, and the excess of mercury sticking to the silver disk was afterwards knocked off. A thin liquid mercury film is then formed. Then a gradual change of the mercury film will take place due to a slow formation of an amalgam film on the surface. Such electrodes cannot be used for determination of

Fig. 1. A mercury/silver electrode; 1) electrode body; 2) Agwire; 3) Hg-meniscus or drop; 4) Ag-disk; 5) special adhesive material. From [38] by permission.

Fig. 2. Scheme of the used metal solid amalgam electrodes: 1) electrode body; 2) Pt-wire; 3) mercury meniscus; 4) solid amalgam. From [44] by permission.

metals at trace levels only, but also for analytical work on reducible organic and biological compounds like DNA [38 46]. As pointed out in [44], the earlier version is actually a nonequilibrium electrode with less stability. The newer version, however, is not using a metal substrate directly connected to the mercury layer, but this is performed in two steps, the electrode with the metal powder is dipped into liquid mercury, and then polished after some time, and then dipped into liquid mercury once more. Consequently, we have the following situation: The platinum wire inside the electrode is in contact with silver powder, somewhat hardened due to some reaction with mercury from the first dipping sequence. This amalgamation, however, is not complete. At the polished end of the electrode, the amalgamation has proceeded further, and this polished surface is brought in contact with mercury from the second dipping sequence. This means that the outer mercury is using more silver, or slightly amalgamated silver, as substrate for the earlier versions of the electrode. But for the newer version, a mixture of silver, mercury and amalgam will be the substrate surface being in contact with the active mercury layer. Consequently, the newer version will give better performance and the electrode can be used for about a week before renewing is needed by dipping it into mercury. This is due to the slower disappearance of the active part of the electrode, the liquid mercury meniscus, over time [38]. In that article it is mentioned: They (the electrodes) are based on solid metal amalgam phase of the dental type according to need modified by a very small amount of mercury. However, as the active part of the electrode is mercury, and the idea by the duplicate dipping procedure is to maintain that mercury, this is actually a convenient design of a
Electroanalysis 2003, 15, No. 8

682 mercury electrode and not a dental type electrode. Such electrodes will be discussed, and compared with in the following.

. Mikkelsen, K. H. Schrder

3.2. Dental Amalgam Electrodes The use of electrodes in voltammetry with more than one active compound has not previously been very much studied in voltammetry. It seems in general that it has been assumed that such an electrode should be pure, consisting of one element only. As pointed out above, mercury is unique as electrode material in analytical voltammetry. Due to the restrictions of using mercury, in particular for off-laboratory use, the present authors attempted to find alternative materials, dental amalgam being an actual candidate. In dental amalgam, mercury is bound up as a stable Ag2 Hg3 alloy in an excess of silver, making it totally nontoxic for analytical purpose. The uses of such small electrodes for soil and groundwater analyses are obviously without any environmental hazard. Investigations of groundwater close to cemeteries [47] have not shown any increased levels of mercury, illustrating its stability in the environment. Also, not to forget, hundred of millions of people are today living with such fillings in their mouths. A great advantage of using dental amalgam as electrodes in analytical voltammetry is that the technique dealing with the material is well established from dental clinical practice and advanced equipment for preparation of proper amalgams is available commercially. As pointed out above, formation of the amalgam can be a slow process, but this can be carried out in minutes using modern dental amalgam mixing equipment and a proper ratio between silver and mercury [48]. With such equipment, air bubbles trapped into the solidified amalgam are avoided, as this will increase the background current. A suitable ratio between silver and mercury should be 1 : 1 by weight (mole ratio 1.85). In our laboratories we normally use 2.5 g fine silver powder (< 50 m) and 2.5 g of analytical grade mercury. This mixture is transferred into a mixing capsule by first introducing the mercury and then the silver powder. The capsule is then installed in a dental amalgam mixer (e.g., ESPE ROTOMIX) and mixed for 12 seconds and centrifuged for 3 seconds. Immediately after the mixing process is ended the amalgam paste is filled into the electrode holder as shown in Figure 3, just as filling a tooth cavity, and a copper wire is inserted in the upper part of the material as electrical connector. After some minutes the amalgam has solidified, but should be kept for at least one day for completing the reaction before polishing to a mirrorlike surface. Several years ago the dentists mixed the silver or the silver alloy and mercury using a mortar and pestle, with a very nonhomogeneous amalgam as the result. Obviously, this will be even more the case with a dipping sequence with no mixing, as mentioned above [44], this being analogous to filling a tooth cavity with silver powder followed by sealing with a drop of mercury.
Electroanalysis 2003, 15, No. 8

Fig. 3. Cross-section of the dental amalgam electrode. From [50] by permission.

Fig. 4. Detection of zinc on a working electrode containing a non-zinc (high copper non-gamma 2-alloy) amalgam for dental use. Analyses performed as differential pulse anodic stripping voltammetry, scan rate 10 mV/s, pulse height 70 mV, deposition time 120 s. The concentrations were 100 ppb, 300 ppb, 400 ppb, 1000 ppb and 1500 ppb. From [50] by permission.

Our first presentation, after patenting, of the dental amalgam electrode was given at the ESEAC meeting in June 2000 [49], not after the Czech appearance of [39] in December 2000, as it is written in [44]. Preliminary experiments were carried out using lost dental fillings from the present author [50]. This indicated that the dental amalgam had sufficient overvoltage vs. hydrogen formation to be useful analytically. However, most of the material for dental purposes also contains additional material, like zinc etc. This is done to improve the dental filling properties. The starting alloy was therefore modified to be silver only [51 55], this also being an approved alloy for making dental amalgam. Results from determination of zinc for one of the first measurements with a standard dental alloy (high copper non-gamma 2) are given in Figure 4. As found from the

Amalgam Electrodes

683

Fig. 5. Measurement of heavy metals in old tap water by differential pulse stripping voltammetry. Solid line shows the real sample, dashed line shows same sample after addition of 100 ppb Zn, 50 ppb Pb and 500 ppb Cu. Predeposition was 120 s at 1450 mV, followed by a scan to 20 mV. Modulation pulse: 50 mV, scan rate: 15 mV/s. Zinc observed at 1100 mV, lead at 450 mV and copper at 150 mV.

Fig. 6. Adsorptive cathodic stripping voltammetry detection of Ni(II) and Co(II) (10, 20, 30 ppb) as dimethylglyoxime complex in NH4Cl buffer solution. Iminodiacetate was added to enhance the cobalt response. Deposition times 30 s at 0.7 V, scan from 0.7 to 1.25 V, pulse height 50 mV. From [52] by permission.

figure, the overpotential is shifted to allow these measurements. A simultaneous determination of zinc, lead and copper in tap water using pure silver only in amalgamation is shown in Figure 5. Measurements of thallium are very convenient by using a dental amalgam electrode. This is important due to frequently high concentration of that element in wastewater from metallurgical industry. The amalgam electrode has been found to give a very good sensitivity towards thallium, with a detection limit in the low ppb to ppt range with 180 s deposition time. The peak potentials for thallium is slightly more positive than that of cadmium, therefore if cadmium and thallium are both present in a solution cadmium may be separated by complexing the cadmium with CN.

The results reviewed above were carried out using anodic stripping voltammetry. By using cathodic stripping or adsorptive stripping techniques, the applications of dental amalgam electrodes can be further expanded. Analyses of nickel and cobalt were performed as adsorptive cathodic stripping voltammetry by use of dimethylglyoxime and iminodiacetate in ammonium buffer solutions. In this solution nickel and cobalt yielded well-defined peaks with good resolution from hydrogen evolution. Figure 6 shows a simultaneous detection of nickel and cobalt at different concentrations. As an example of using dental amalgam electrodes for measuring heavy metals in beverages a procedure was introduced in [54]. In contrast to measurements using HMDE, the method of medium exchange cannot be used directly when a dental amalgam electrode is applied because this causes an unpredictable loss of material due to oxidation. We therefore introduced: Online Medium Exchange (OME) with the stripping medium, by performing the exchange in a flow system maintaining the deposit potential [54]. Obviously, this technique can also be applied directly for flow systems. Dental amalgam voltammetry for remote control seems very promising and is now applied for continuous environmental monitoring. Figure 7 shows a typical example from a real sample from the outlet air scrubbing wastewater, from a waste incineration plant in Trondheim, Norway. As found from the results discussed above, the properties of dental amalgam electrodes are very similar to silver electrodes, but with one very essential exception, the overvoltage for formation of hydrogen is much higher. This is not as high as for mercury, but sufficiently high for a voltage window to measure zinc and other compounds. It is of interest to compare the dental amalgam electrode and co-workers. with the electrodes developed by Novotny They wanted to construct an electrode covered with a stable
Electroanalysis 2003, 15, No. 8

684

. Mikkelsen, K. H. Schrder

Fig. 7. Plot from continuous remote monitoring of zinc, cadmium and lead from Heimdal Waste Incineration Plant in Norway. To the scrubbing wastewater was added NH4Cl (to 0.05 M). Differential pulse anodic stripping voltammetry, 120 s deposit time at 1300 mV, scan rate 15 mV s1, differential pulse 50 mV.

mercury layer or a stable mercury meniscus as the active part. In their earliest versions this stability was not as good as wanted because slow amalgamation of the mercury meniscus from reaction with the substrate being silver wire. However, in their newer versions this reaction proceeds much slower because the substrate, a mixture of silver, mercury and amalgam already contains a more complete amalgam and is stable towards reacting with more mercury. On the other hand, the dental amalgam electrode has properties more like the silver electrode with extended potential window. It can also be polished without any change in its properties. As discussed next, a silver/mercury alloy with a few percent of mercury only, also behaves like a silver electrode, with an analogous extension of the potential window [56]. This further supports this view. The dental amalgam seems to combine some of the properties of the silver electrode with those of the mercury electrode. For instance, the dental amalgam material (Ag2 Hg3 in silver) is a solid electrode, and solid deposits are formed. On a mercury drop, mercury film or mercury meniscus electrode, however, liquid mercury amalgams are formed. Since the dental amalgam electrode is a solid electrode, formations of intermetallic compounds are observed to a greater extent than for liquid mercury. For instance, in solutions containing both zinc and copper, the formation of zinc-copper intermetallic compound is observed and contemporary a significant decrease in the response for zinc is observed. However, by addition of chloride to the solution, this intermetallic compound has been avoided, due to formation of a copper (I) chloride complex, which prevents zinc to form an intermetallic compound. As known, the solubility of cadmium is greater than the solubility of lead in mercury, and consequently a better response for cadmium is observed when diluted amalgams are formed in the mercury drop electrode [52]. However, at the dental amalgam electrode, where solid deposits are
Electroanalysis 2003, 15, No. 8

formed, lead shows a better response than cadmium. This is a typical silver behaviour, and this unique affinity seems to be maintained in the dental amalgam alloy. At a potential of about 200 mV, an anodic current is observed using dental amalgam electrodes, most likely due to oxidation of the dental amalgam. As solid, nontoxic material, the dental amalgam can be used in remote online analyses in the field. After optimizing of the procedures, the detection limits for the metals are assumed to be in the same range as for the mercury and mercury film electrode. It can also be used repeatedly over a long period of time without any maintenance, which is essential for remote, online and field apparatus.

3.3. Other Solid Electrodes Several articles have appeared dealing with alternative electrode materials to extend the potential window. As examples are the use of bismuth film [57] and boron doped diamond [58]. Further discussion of such electrodes is beyond the scope of the present article. It seems to have been an established opinion that onecomponent electrodes should be superior for voltammetric analyses. The use of alloys, adding some percent of a second metal, is not extensively studied in order to obtain an extended potential window. In the battery industry, however, more component alloys are frequently used in order to avoid hydrogen gas formation. The present authors have studied silver electrodes with a few percent of mercury, bismuth and lead oxide [56, 59], all with the effect of extending the actual potential window, and it is reasonable to assume that other main metals than silver, with small quantities of other components will have corresponding effect. Discussion of the use of other additives than mercury will be beyond the scope of the present article.

Amalgam Electrodes

685

Fig. 8. Detection of zinc on silver with 4% mercury alloy electrode. The zinc concentration was 100, 200, 300 and 400 mg L1. All scans were performed in DPASV mode in NH4Ac (0.05 M). Scan rate: 15 mV s1, pulse height: 70 mV, and deposition time: 2 min. From [51] reproduced by permission of the Royal Society of Chemistry.

The technique for making such alloys with a few percent of mercury differs substantially from the way to make dental amalgam electrodes because dental clinical procedures cannot be applied, as no homogeneous solidification will take place after the mixing. One way is to take the silver powder and the actual quantity of mercury in a quartz tube, seal it by heating the upper part, followed by melting and mixing the alloy. After cooling, the alloy is made as a small cylinder, being the active part of the electrode after polishing. Figure 8 shows measurements of zinc by use of a silver electrode containing 4% mercury. As found from the figure, the potential window is shifted towards a sufficiently negative value to allow the determination of zinc and other species. Addition of 400 mg L1 cadmium to solutions mention above did not show any significant influence on the response of the zinc peak. Further results [59] indicate that the extension of the potential window increases with the fraction of mercury or other additives, with pure mercury at present with the largest negative value. Thus the amount of the additive can be tailored for the actual analytical problem. However, much more work still remains in this field.

4. Summary and Future Directions

Dental amalgam (Ag2Hg3 as the main compound) seems to be a promising electrode material for use in voltammetry. The solid dental amalgam electrode combines the properties from mercury with some of the properties of silver. The alloy has a high overvoltage towards hydrogen, and shows particular good sensitivity towards zinc, lead and iron. But

also other metals like, e.g., nickel, cobalt, cadmium, and thallium can be detected in the low ppb to sub ppb area. The deposition of metals onto the dental amalgam surface is greatly characterized by the fact that it is a solid material and shows therefore a great difference from the pure mercury electrode, e.g., in respect to formation of inter metallic compounds. However the most common intermetallic compounds may be avoided by addition of a third element or compound. At 200 mV an anodic current is observed, most likely due to a decomposition of the dental amalgam. Dental amalgam is a solid, nontoxic material, and this makes it possible to be used in online analyses in the field. The detection limits for the most metals are assumed to be in the same range as for the mercury or mercury film electrode. The stability over time has been found to be good (several weeks) without any maintenance, which is essential for online and field apparatus. Also, it is easy and cheap to manufacture such electrodes, using techniques well established for dental clinics. Potentiometric stripping analysis (PSA) is a simple, but very sensitive and important part of electroanalytical chemistry. PSA was presented several decades ago [60], but it has not obtained as much attention as it deserves. The stripping procedure is in general performed in two different ways, 1. By oxidation using chemicals, most frequently used with the presence of oxygen, or 2. By constant current oxidation. The latter is normally preferred because more standardized conditions are obtained. Amalgam electrodes are very useful for PSA analyses for the same reasons as given for voltammetry. This method is very convenient for remote and off-laboratory use. Preliminary investigations indicate dental amalgam to be a very promising material for such purposes and further developments are in progress in our laboratories.
Electroanalysis 2003, 15, No. 8

686 A general disadvantage by using amalgam electrodes is the short potential window in the positive voltage range. Certainly, most of the actual measurements are at negative potentials, but many are also at more positive values, but developing cathodic as well as anodic procedures can in many cases solve this. Future directions are expected to be in the development of new techniques, with new electrode materials like two and more component alloys, and conducting polymers. Another promising direction, verified from our preliminary experiments, is to modify the dental amalgam by adding small amounts of ion exchanger before it solidifies. Increase in sensitivity and selectivity is then achieved. A great number of analytical methods have been developed during the last years, but very few of those methods are actually in daily use to solve real problems. In particular this is the case for off-laboratory applications. It is a great distance from developing a method used in a laboratory tested on pure materials, to continuous outdoor measurements. For that reason such monitoring is still limited to a few and very simple parameters. Voltammetry and PSA are very convenient for such monitoring, but the long-term stability is a critical factor. Thin-film electrodes, like mercury film, are useful for many applications, but for continuous measurements the homogeneous electrodes, like silver and dental amalgam, have advantages due to longterm stability. It has been found that the dental amalgam electrode in most cases can be used to detect the same analyte in the same matrix as for the mercury drop electrode, therefore it is expected that the dental amalgam electrode as well as the alloy electrodes also will be suitable for use in analytical work on reducible organic and biological compounds as, e.g., DNA. This will be investigated later. As mentioned above, such dental amalgam electrodes and alloy electrodes are quite stable over time without any maintenance. It is only needed to polish the electrodes monthly for some seconds with a filter paper when monitoring drinking water, and more frequently for polluted water, in order to avoid electrode fouling. However, for remote monitoring it is of interest to extend this period. Again a technology with a scaling developed for dental practice can be applied. From time to time, such homogeneous electrodes can be automatically treated like removal of tooth stones and plaque in dentistry [61]. We have recently started investigations in these lines, with very promising results. This will be reported later. Finally, additionally to applying low frequency sound of about 80 100 Hz [49, 62] it is very convenient for offlaboratory use with increased sensitivity. Better understanding of the nature of overpotential and underpotential reactions is of great interest, not only from a theoretical point of view, but also as a tool for improved electrode development. Finally, the development of devices for miniature measurements will be important in the future.

. Mikkelsen, K. H. Schrder

5. References
sek, Modern Techniques in Electroanalysis, Vol. 139, [1] P. Vany Chemical Analysis, Wiley, New York, 1996. [2] P. Zuman, Anal. Lett. 2000, 33, 163. [3] D. A. Payne, A. J. Bard, J. Electrochem. Soc. 1972, 119, 1665. . Komorsky-Lovric, A. M. Bond, J. Electroanal. [4] M. Lovric, S Chem, 1991, 319, 1. [5] L. K. Bieniasz, J. Electroanal. Chem, 2002, 527, 21. [6] L. Airey, Analyst 1947, 72, 304. [7] J. Wang, Analytical Electrochemistry, 2nd ed, Wiley-VCH 2000, pp. 107. [8] G. T. Cheek, T. Graham, W. E. OGrady, Proc. Electrochem. Soc. 1994, 94. [9] M. Ciszkowska, M. Donten, Z. Stojek, Anal. Chem. 1994, 66, 4112. [10] K. R. Wehmeyer, R. M. Wightman, Anal. Chem. 1985, 57, 1989. [11] M. A. Baldo, S. Daniele, C. Bragato, G. A. Mazzocchin, Anal. Chim. Acta 2002, 464, 217. [12] S. P. Kounaves, W. Deng, J. Electroanal. Chem. 1991, 301, 77. [13] R. R. De Vitre, M. L. Tercier, M. Tsacopoulos, J. Buffle, Anal. Chim. Acta 1991, 249, 419. [14] W. Lu, A. S. Baranski, J. Electroanal. Chem. 1992, 335, 105. [15] M. Ciszkowska, Z. Stojek, J. Electroanal. Chem. 1985, 191, 101. [16] P. J. Brendel, G. W. Luther III, Environ. Sci. Technol. 1995, 29, 751. [17] G. W. Luther III, C. E. Reimers, D. B. Nuzzio, D. Lovalvo, Environ. Sci. Technol. 1999, 33, 4352. [18] G. W. Luther III, P. J. Brendel, B. L. Lewis, B. Sundby, L. Lefranois, N. Silverberg, D. B. Nuzzio, Limnol. Oceanogr. 1998, 43, 325. [19] M. Huettel, W. Ziebis, S. Forster, G. W. Luther III, Geochim. Cosmochim. Acta. 1998, 62, 613. [20] M. E. Dollhopf, K. H. Nealson, D. M. Simon, G. W. Luther III, Mar. Chem. 2000, 70, 171. [21] M. Taillefert, G. W. Luther III, D. B. Nuzzio, Electroanalysis 2000, 12, 401. [22] G. W. Luther III, T. F. Rozan, M. Taillefert, D. B. Nuzzio, C. DiMeo, T. M. Shank, R. A. Lutz, S. C. Cary, Nature 2001, 410, 813. [23] P. Anschutz, B. Sundby, L. Lefranois, G. W. Luther III, A. Mucci, Geochim. Cosmochim. Acta 2000, 64, 2751. [24] M.-L. Tercier, J. Buffle, F. Grazoittin, Electroanalysis 1998, 10, 355. bert, M.-L. Tercier, J. Buffle, G. C. Fiaccab[25] C. Belmont-He rino, N. F. deRooij, M. Koudelka-Hep, Anal. Chem. 1998, 70, 2949. [26] M.-L. Tercier, J. Buffle, Anal. Chem. 1996, 68, 3670. [27] R. R. DeVitre, M.-L. Tercier, M. Tsacopoulos, J. Buffle, Anal. Chim. Acta 1991, 249, 419. [28] M.-L. Tercier, N. Parthasarathy, J. Buffle, Electroanalysis 1995, 7, 55. [29] C. Belmont, M.-L. Tercier, J. Buffle, G. C. Fiaccabrino, M. Koudelka-Hep, Anal. Chim. Acta 1996, 329, 203. [30] M.-L. Tercier, J. Buffle, Electroanalysis 1993, 5, 187. [31] O. C. Keller, J. Buffle, Anal. Chem. 2000, 72, 936. [32] B. Bas, Z. Kowalski, Electroanalysis, 2002, 14, 1067. [33] E. Fischer, C. M. G. van den Berg, Anal. Chim. Acta 1999, 385, 273. [34] D. A. Fungaro, C. M. A. Brett, Anal. Chim. Acta 1999, 385, 257. [35] S. B. Khoo, S. X. Guo, Electroanalysis 2002, 14, 813. [36] E. Fischer, C. M. G. van den Berg, Anal. Chim. Acta 2001, 432, 11.

Electroanalysis 2003, 15, No. 8

Amalgam Electrodes [37] J. Galvez, K. H. Schrder, J. Electroanal. Chem. 1993, 361, 121. , L. Havran, B. Yosypchuk, M. Fojta, Electro[38] L. Novotny analysis 2000, 12, 960. , B. Yosypchuk, Chem. Listy 2000, 94, 1118. [39] L. Novotny , US-CZ Workshop on Electro[40] B. Yosypchuk, L. Novotny chemical Sensors, Czech Chemical Society, Prague 2001, p. 26. , B. [41] K. Peckova, J. Barek, M. Drevinek, T. Navratil, L. Novotn Yosypchuk, S. Vaingatova, J. Zima, US-CZ Workshop on Electrochemical Sensors, Czech Chemical Society, Prague 2001, p. 32. , Crit. Rev. Anal. Chem. 2002, 32, [42] B. Yosypchuk, L. Novotny 141. , Electroanalysis 2002, 14, 1138. [43] B. Yosypchuk, L. Novotny , Talanta 2002, 56, 971. [44] B. Yosypchuk, L. Novotny , Chem. Listy 2002, 96, 756. [45] B. Yosypchuk, L. Novotny , L. Novotny , E. [46] F. Jelen, B. Yosypchuk, A. Kourilova Palecek, Anal. Chem. 2002, 18, 4788. [47] M. Eiskjaer, D. Arenholdt-Bindslev, J. Dent. Res. 1994, 73, 981. [48] E. H. Greener, J. K. Harcourt, E. P. Lautenschlager, Materials Science in Dentistry. Williams & Wilkins, Baltimore 1972. ch. 8. [49] . Mikkelsen, K. H. Schrder, The 8th Int. Conf. ElectroAnalysis (ESEAC 2000). Bonn, Germany, 2000. http:// www.chem.ntnu.no/  knusch/bonnposter.pdf

687
[50] . Mikkelsen, K. H. Schrder, Analy. Lett. 2000, 33, 3253. [51] . Mikkelsen, K. H. Schrder, Electrochemistry and Interfacial Chemistry in Environmental Clean-Up and Green Chemical Processes, Coimbra, Portugal, 2001. [52] . Mikkelsen, K. H. Schrder, T. A. Aarhaug, Collection of Czechoslovak Chemical Communications 2001, 66, 465. [53] . Mikkelsen, K. H. Schrder, Environmental and Health Aspects of Mining, Refining and Related Industries, Skukuza, Kruger National Park, South Africa, 2001. [54] . Mikkelsen, K. H. Schrder, Anal. Chim. Acta 2002, 1, 249. [55] . Mikkelsen, K. H. Schrder, 9th International Conference on Electroanalysis European Society for Electroanalytical w, Poland, 2002. Chemistry, Krako [56] . Mikkelsen, K. H. Schrder. Analyst 2000, 125, 2163. [57] J. Wang, J. Lu, Electrochemistry Communications 2000, 2, 390. [58] Y.-C. Tsai, B. A. Coles, K. Holt, J. S. Foord, F. Marken, R. C. Compton, Electroanalysis 2001, 13, 831. [59] . Mikkelsen, K. H. Schrder, M. Skogvold, L. T. Findalen, 9th International Meeting on Chemical Sensors. Boston USA, 2002. http://www.chem.ntnu.no/  knusch/alloyposter.pmd [60] D. Jagner, Trends Anal. Chem. 1983, 2, 53. [61] http://www.dentalnet.no/produkt/EMS [62] . Mikkelsen, K. H. Schrder, Electroanalysis 1999, 11, 504.

Electroanalysis 2003, 15, No. 8