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Versatile ow injection manifold for analytical calibration

Pawe Koscielniak , Marcin Wieczorek, Joanna Kozak, Magorzata Herman Department of Analytical Chemistry, Jagiellonian University, R. Ingardena 3, PL-30-060 Krakow, Poland

a r t i c l e
Article history:

i n f o

a b s t r a c t
A ow injection calibration system, originally designed and tested in our laboratory, is presented here as a versatile analytical tool serving for calibration purposes. It is characterized by a simple construction, easy operation and the possibility of offering rich measurement information with the use of a single standard solution. It is shown that depending on instrumental conditions and the composition of the calibration solutions the manifold is able to realize various calibration procedures according to interpolative, extrapolative and integration modes. As an experimental example, the determination of calcium in the cabbage sample by ame atomic absorption spectrometry has been calibrated by means of dilution method (DM) in the integration mode. 2007 Elsevier B.V. All rights reserved.

Received 13 October 2006 Received in revised form 20 December 2006 Accepted 4 January 2007 Published on line 13 January 2007 Keywords: Calibration Flow injection analysis Dilution method

1.

Introduction

Recently, a novel classication of the empirical calibration methods has been proposed (see Table 1) [1,2]. According to this classication four calibration methods being different from each other in terms of both preparative and interpretative manners are specied: (a) the conventional method (CM), (b) the indirect method (IM), (c) the internal standard method (ISM) and (d) the dilution method (DM). Furthermore, each of them can be performed in interpolative, extrapolative and integrated modes. The conventional calibration method is commonly used in analytical practice in two modes: interpolative and extrapolative, which are usually termed the calibration curve method and the standard addition method, respectively. In the rst case the calibration graph is prepared with the use of a set of standard solutions prepared separately from a sample; as a consequence, the signal measured for the sample is then related to the calibration graph and the analytical result is calculated in the interpolative way. In the later case the standard solutions are added to the sample, hence the calibration graph is limited by the signal obtained for the sample

and the analytical result can be evaluated exclusively in the extrapolative way. Since the analyte is able to be measured in original sample environment (including interferents), the extrapolative approach in contrast to the interpolative one represents, in principle, a way of compensation of interference effects. IM and ISM are applied to calibration in the interpolative mode. IM is used when the analytical signal is not possible to be measured for the analyte but for a substance, which can enter a chemical reaction with the analyte. A constant amount of such a reagent is added both to the sample and to the standard solutions. When measuring the signals in every standard solution for the reagent remaining after reaction, the calibration graph can be constructed allowing the analyte to be determined in the interpolative way. Calibration by means of IM contributes to the enlargement of the number and types of analytes that can be determined with the use of a given analytical instrument; typical examples can be found concerning atomic absorption spectrometry [3]. In ISM the standard solutions and the sample are supplemented with a constant amount of a substance (internal standard) being similar to the analyte in terms of physico-

Corresponding author. Fax: +48 12 634 05 15. E-mail address: koscieln@chemia.uj.edu.pl (P. Ko scielniak). 0003-2670/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.aca.2007.01.001

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Table 1 Novel classication of the calibration methods and their applicability (+++, ++, + or ) in analytical practice Kind of the method Interpolative
Conventional method (CM) Indirect method (IM) Internal standard method (ISM) Dilution method (DM) +++ ++ ++ +

Character of the method Extrapolative

+++ +

Integrated
+

chemical properties [4]. The calibration graph is based on the analytical signals measured as the ratio of signals obtained for the analyte and for the internal standard and then the analytical result is found interpolatively. The principal objective of ISM is the analyte determination with increased precision: if the size and direction of random changes of both component signals are similar, the uctuations of the proportion of both signals has a chance to be smaller than of each single signal and, consequently, the random error of the analytical result can be minimized. In the literature several reports can be found about the calibration by the dilution method realized in both interpolative [5,6] and extrapolative [7,8] mode. According to this method a sample and a single standard solution, either prepared separately from the sample or added to it, are progressively diluted and they are exposed to measurements at every dilution stage. Each pair of signals obtained allows the analyte to be determined either in interpolative or extrapolative ways, respectively, with the aid of two-point calibration graph. If the interferents are present in the sample assayed it is believed that the interference effect has a chance to be progressively reduced with the sample successively diluted and, consequently, the analyte concentration found in the sample of possibly great dilution is assumed to be the nal analytical result. Lately, the concept of the integrated calibration mode has been developed in our research group [1,9]. Namely, it has been suggested to perform analytical calibration in accordance to the procedure integrating the interpolative and extrapolative conventional methods. Such a procedure permits to construct two or even more (but not a single as commonly) calibration graphs and, consequently, to nd the analytical concentration in a sample in interpolative and extrapolative ways simultaneously. It has been proved that the obtained particular estimations of the analytical result can be mutually compared and veried giving a chance to evaluate the nal analytical result with improved accuracy [10]. As revealed, each of the calibration approaches mentioned above is characterized by own specic usefulness in analytical chemistry and can be used for solving different problems and difculties in various analytical circumstances. However, as seen in Table 1, most of these methods are used in analytical practice only occasionally. The reasons of such a situation can be found to be very different [1] but one of them is certainly a lack of an analytical instrumentation being versatile enough to realize the calibration method optionally chosen. Another question is that some of the calibration approaches shown in Table 1 are not known among analysts at all, however, they are theoretically predicted by the proposed classication and believed to be applicable.

In our laboratory, various ow injection calibration systems have been recently designed and tested [911]. In the present paper, the ow manifold of the greatest versatility in terms of adaptation to various calibration purposes is shown. It is presented how the manifold is designed and operated, as well as the conditions are dened allowing all calibration methods mentioned above to be realized in different modes. It is also proved experimentally that the dilution method in the integration mode can be performed effectively with use of the manifold designed.

2.
2.1.

Flow injection calibration manifold

Design and operation

The scheme of the manifold is presented in Fig. 1. It consists of: (a) one or more pumps, P, propelling four streams of calibration solutions from the sample, S, standard, ST, and carrier, C, reservoirs with ow rates p, q and r and (b) eight-channel two-positional injection valve, V, equipped with four injection loops, , , and , and operated in two positions: I (shown in Fig. 1) and II, i.e. when the rotor (dashed circle) is rotated 45 counter-clockwise in relation to stator (solid circle). When valve V is initially situated in position I, solutions ST, S and C are directed in the form of continuous streams to reservoirs ST and S, and to the detector, respectively. If the valve is rotated to position II and back to position I, solutions ST and S are injected to solution C, propelled with ow rates p and q through tubes L1 and L2 to tube L3 , mixed with each other and directed to the detector. At the same time solution C is injected to solutions ST and S, and then propelled with rate r towards valves V1 and V2 . This general operation of the system is described in details in Table 2.

2.2.

Versatility in terms of operation

Different instrumental parameters of the manifold can be xed allowing various effects to be gained (see Fig. 1): Depending on the volumes of loops , , and , and of tubes L1 and L2 , injected zones of solutions ST and S can be directed to tube L3 separately from each other, or they can be merged with each other either partly or totally. If rate p is equal to rate q, solutions owing through tubes L1 and L2 are mutually diluted in tube L3 to the same extent, but if p = q, they are diluted with each other differently with dilution factors P = p/(p + q) and Q = q/(p + q), respectively. Depending on the positions of valves V1 and V2 the manifold can work in three different congurations: (a) opened,

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Fig. 1 Versatile calibration ow injection manifold: C, St, S: the carrier, standard and sample reservoirs, respectively; W: waste; P: pump; V: injection valve; V1 , V2 : directive valves; Det: detector; , , , : injection loops; L1 , L2 , L3 : transfer tubes; p, q, r: ow rates.

when the solutions aspirated from both reservoirs, ST and S, are directed to the waste (see Fig. 1), (b) half-closed, when solution ST is directed back to its reservoir but solution S is directed to the waste and (c) closed, when both solutions, ST and S, are directed back to their reservoirs. As a consequence, if the system works in the half-closed conguration, solution C injected from loops and to solution ST is mixed with this solution in its reservoir but in the closed conguration solution C injected from loops and to solution S is additionally mixed with solution S in its reservoir. Injection valve V can be rotated in turn from positions I to II and back allowing in the subsequent operation cycles successive injection of solutions ST and S to solution C and their transportation towards detector, as well as successive injection of solution C to solutions ST and S and its transportation either to the waste or to their reservoirs.

2.3.

Versatility in terms of calibration

Due to operative versatility the manifold can be used for realization of different calibration purposes as follows:

If the standard (ST) and sample (S) solutions, both injected to the carrier stream (C), reach the detector in the form of zones situated separately from each other or partly merged with each other (as seen in Fig. 2), the analytical signals can be measured for the analyte in: (a) the standard and the sample, (b) the sample and the standard added to the sample and (c) the standard, the sample and the standard added to the sample. Then, the measurement information obtained in positions I and II of the injection valve are the same but sufcient to perform calibration according to conventional method in the interpolative, extrapolative and integration modes, respectively, using two-point calibration graphs. The instrumental conditions allowing the zones to be situated with each other adequately to particular calibration purposes are given in Table 3. If, in addition, rate p is not equal to rate q, the standard and sample zones are diluted differently with the carrier and with each other in positions II and I of the injection valve. As a result, each of zone congurations mentioned above is characterized by not a single but two different sets of analytical signals and, consequently, the analyte concentration in the sample can be estimated by double results (see Table 3).

Table 2 Detailed operation of the ow manifold in initial position (I) of the injection valve and in a single cycle of rotating this valve to position II and back (compare Fig. 1) Cycle
0

Position of valve V
I

Solution
ST S C

Injection
No No No No C C ST S C C ST S

Flow rate
r r p q p q r r q p r r

Flow path
V1 V2 L1 L3 Det L2 L3 Det L1 L3 Det L2 L3 Det V1 V2 L2 L3 Det L1 L3 Det V1 V2

II

ST S C

ST S C

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Fig. 2 The scheme presenting of how the standard (ST) and sample (S) zones injected to the carrier stream (C) can be situated in tube L3 to produce signals for the analyte in the standard (R1 ), in the sample (R2 ) and in the standard merged with the sample (R3 ), which are used for calibration by the conventional method in the following modes: (a) interpolative, (b) extrapolative and (c) integrated.

If the manifold is used in the half-closed conguration and the calibration is performed in more than a single cycle (compare Table 2), the standard solution has a chance do be progressively diluted by the carrier zones directed towards the ST reservoir. As a consequence, a set of standard solutions of decreasing analyte concentrations are produced and directed to the detector in successive measurement cycles, hence the calibration graphs constructed are able to be based not only on two but on several measurement points. If the role of the carrier stream is played by the solution with reagent producing (instead of the analyte) the analytical signal and the same reagent in the same concentration is added to the standard and sample solutions, the calibra-

tion performed by the manifold is in accordance with the indirect method (see Table 4). If the role of the carrier stream is played by the solution with an internal standard, which is also added in the same concentration to the standard and sample solutions, the calibration performed by the manifold is in accordance with the internal standard method (see Table 4). If the manifold is used in the closed conguration and the calibration is performed in more than a single cycle, both the standard and sample solution are progressively diluted by the carrier zones directed towards the ST and S reservoirs, respectively. In such a situation the calibration by the dilution method is able to be performed (see Table 4 and the experimental example shown below).

Table 3 Instrumental conditions (dened by parameters p, q, , , , , L1 , and L2 ; compare Fig. 1) allowing the calibration methods to be performed in different modes with different numbers of estimations of the analytical result Instrumental conditions Mode of the method and number of estimations obtained p=q
= = = < L2 , L2 > L1 , L1 = min > , > , = , = , L1 = L2 = min = = = > L2 , L2 > L1 , L1 = min Interpolative, 1 Extrapolative, 1 Integrated, 2

p>q
Interpolative, 2 Extrapolative, 2 Integrated, 4

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Table 4 Instrumental conditions of calibration manifold (dened by the solutions aspirated from different reservoirs in the system of opened (OP), half-closed (HC) or closed (CL) conguration) allowing the calibration to be performed by different methods Solution owing trough a given reservoir Standard reservoir
Standard Standard + Ra Standard + ISb Standard
a b

Conguration Carrier reservoir

Neutral carrier R IS Diluent OP or HC OP or HC OP or HC CL

Calibration method

Sample reservoir
Sample Sample + R Sample + IS Sample

CM IM ISM DM

R, Reagent producing analytical signal. IS, Internal standard.

3.

Experimental

Standard stock solutions containing calcium at a concentration of 1 mg mL1 were prepared from Titrisol standards (Merck, Germany). The standard solution used for calibration was made up by mixing and dilution of the stock solutions with 1% HNO3 (v/v). In order to prepare the cabbage sample a portion of ca. 0.5 g of a cabbage leaf (initially dried, ground and homogenated) was digested in a microwave oven with 6 mL of concentrated HNO3 (Merck, Germany) and 1 mL of concentrated HClO4 (Merck, Germany). Digestion condition was applied as 60, 85 and 100% of max. power (600 W) for 5, 5 and 10 min, respectively. After digestion, the sample solution was cooled in the air down to the temperature of 25 C, transferred into 100 mL volumetric ask, and diluted to the mark with 1% HNO3 (v/v). All reagents used were of analytical grade. Doubly deionised water was used throughout. Measurements were carried out on Perkin-Elmer 3100 atomic absorption spectrometer (Perkin-Elmer, USA). The airacetylene ame was used. The nebuliser free uptake rate was 7.2 mL min1 . A calcium hollow cathode lamp was operated at 7 mA. The wavelength was set to 422.7 nm with a spectral slit width of 0.7 nm. An IBM compatible PC-AT computer was connected to the spectrometer for data handling with a time resolution of 20 ms. The ow calibration system used through the experiments were composed of a ow injection module FIAS 100 (PerkinElmer, USA) equipped with multichannel peristaltic pump and eight-channel two-positional injection valve, as well as of a piston pump SNK DMX-2000 (Sanuki, Japan). The Tygon tubings were installed in the peristaltic pump and the PTFE tubings (0.8 mm i.d.) were used for all connections, loops, coils and tubes.

tal parameters (see Fig. 1): = = = = 3.78 mL, L1 = 0.05 mL, L2 = 0.70 mL, L3 = 0.50 mL, p = 5.1 mL min1 , q = 3.0 mL min1 . A sample (S) was the cabbage sample of unknown calcium concentration, the standard solution (ST) contained calcium in concentration of 4.0 or 6.0 mg L1 , but the carrier solution (C) was 1% (v/v) HNO3 . The measurements were performed with the use of ame atomic absorption spectrometer. Entire calibration procedure encompassed ve cycles, i.e. the injection valve was situated initially in position I and then ve times in positions II and I (compare Table 2). Under instrumental conditions established as above the mutual positions of the standard and sample zones, when achieving the detector in each calibration cycle, as well as the corresponding recording picture obtained were as schematically presented in Fig. 3. Both zones were of the volumes great enough to create local steady-state fragments on two multiple injection peaks produced, hence as many as seven analytical signals, R0 R6 , of different values were possible of measuring accurately. On the basis of this set of signals four two-point calibration graphs were able to be constructed (see Fig. 4) allowing four estimations, cx1 cx4 , of the analytical result to be calculated from the following formulas: cx1 = cx2 = cx3 = cx4 = R4 cST R1 R3 cST R6 R4 cST R2 R3 R3 cST R5 R4 (1)

(2)

(3)

(4)

4.

Results and discussion

In order to check the performance and usefulness of the ow manifold designed as well as to introduce a novel calibration method to analytical practice it was made an attempt to adapt the manifold to calibration by the dilution method in the integrated mode. For this aim it has been used in the closed conguration with the following instrumen-

where cST is the analyte concentration in the standard solution. As seen in Fig. 4, values cx1 cx4 are considerably different from each other, hence they are not able to estimate the analytical result accurately. It is so because they are calculated from the analytical signals, which are produced by the zones injected from the standard and sample solutions differently diluted in their reservoirs with the carrier solution. In particular, signals R1 R3 shown in Fig. 4 were obtained in rst calibration cycle in position II of the injection valve and they

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11

Fig. 3 The scheme presenting of how the standard (ST) and sample (S) zones can be diluted with each other and with the carrier solution (C) to produce seven different analytical signals (R0 R6 ) when they ow to the detector with different rates (p and q) in two positions of the injection valve (I and II).

were produced by zones injected from undiluted standard and sample solutions (i.e. of the dilution factor k1 = 1). Simultaneously with injection of these solutions they were diluted with the carrier, hence after rotating the valve to position I signals R4 R6 were produced by zones injected from solutions of greatest dilution (k2 = 0.811). In general, the current dilution factor, k2n1 (where n is a number of the calibration cycle) can be calculated for a given calibration solution (standard or sample) when knowing initial volume of the solution in its reservoir, volume of the carrier zone injected to this solution and previous dilution factor value, k2n . In order to make estimations cx1 cx4 theoretically equal to each other (cx1 = cx2 = cx3 = cx4 ) values of the dilution factors should be known and taken in account in formulas (1)(4) as follows: cx1 = cx1 cx2 = cx2 cx3 = cx3 cx4 = cx4 k2n1 k2n k2n k2n1 k2n1 k2n k2n k2n1 (5)

both standard solutions (of calcium concentrations 4.0 and 6.0 mg L1 ) are shown in Table 5. For comparison, ve portions of the same sample of different dilution degree (k = 1.00, 0.60, 0.40, 0.25 and 0.20) were separately prepared and analyzed by the interpolative conventional method, i.e. using a set of six standard solutions (containing calcium from 1.0 to 6.0 mg L1 ) for construction of the calibration curve and calculating the analytical results in the interpolative way. The results are also given in Table 5.

(6)

(7)

(8)

As seen, Eqs. (5) and (6) are of the interpolative character but Eqs. (7) and (8) are of extrapolative character, hence the dilution method was performed in the integration mode indeed. The sample was analyzed three times under the same experimental conditions. The estimations, cx1 cx4 , and their average value, cav , obtained during each of ve calibration cycles repeated three times were averaged. All results (with their condence intervals, = 0.05) obtained with the use of

Fig. 4 Calibration graphs constructed in the rst cycle (k1 = 1, k2 = 0.811) of the calcium determination in the cabbage sample (compare Table 5) and estimations of the analytical result obtained by the interpolative (cx1 , cx2 ) and extrapolative (cx3 , cx4 ) ways.

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Table 5 Results of the calcium determination in the cabbage sample obtained by the interpolative conventional method (with the use of set of standard solutions) and by the integrated dilution method with the use of single standard solutions containing 4.0 (a) and 6.0 (b) mg L1 of calcium
Interpolative conventional method Dilution factor 1.00 Calcium content found (mg L1 ) 4.51 0.08 4.76 0.11 4.91 0.11 4.95 0.27 5.12 0.30 Cycle n Dilution factor k2n1 1 1.000 k2n 0.811 a b a b a b a b a b cx1 4.22 0.35 4.29 0.20 4.66 0.27 4.62 0.37 4.92 0.30 4.90 0.45 4.85 0.20 4.91 0.05 5.11 0.32 4.97 0.84 cx2 4.68 0.27 5.52 0.27 5.03 0.70 5.40 0.30 5.17 0.60 5.26 0.40 5.23 1.42 5.00 1.37 5.36 0.67 4.98 1.57 Integrated dilution method

Calcium content found (mg L1 ) cx3 4.49 0.17 4.49 0.07 4.82 0.40 4.73 0.40 4.95 0.35 4.99 0.47 4.99 0.27 5.00 0.17 5.22 0.32 5.06 1.07 cx4 5.37 0.40 5.72 0.42 5.60 0.65 5.57 0.10 5.56 0.94 5.52 0.57 5.45 1.49 5.42 1.32 5.34 0.70 5.00 1.64 cav 4.69 0.30 5.01 0.22 5.03 0.50 5.08 0.22 5.15 0.47 5.17 0.45 5.13 0.82 5.08 0.70 5.26 0.37 5.00 0.27

0.60

0.658

0.533

0.40

0.433

0.351

0.25

0.285

0.231

0.20

0.187

0.152

5.

Discussion

According to the methodology of the integrated calibration mode concentration values cx1 , cx2 , cx3 and cx4 are characterized by several specic features [10,11]: from among four values, cx1 cx4 , two of them, cx1 and cx2 , are obtained in the interpolative way but two others, cx3 and cx4 , in the extrapolative way, but all of them are theoretically equal to each other, each of values cx1 cx4 is obtained from different set of signals (see Eqs. (5)(8)), hence they are independent from each other, estimations cx1 cx4 are obtained from the signals corresponding to the standard and sample zones, which are diluted mutually and with the carrier stream with dilution factor P or Q (see text above), but they can be found with no information on values P and Q (see Eqs. (5)(8)), because the condition P + Q = 1 is fullled, if relative random uctuations of the signals measured are equal to each other, all four estimations, cx1 cx4 , are obtained with equal relative random errors. If the integrated mode is related to the dilution method, each set of four values cx1 cx4 obtained in each calibration cycle performed with the use of the manifold designed can be considered taking above features into account. As the uctuations of analytical signals recorded in each calibration cycle were statistically equal to each other (test F, = 0.05), all of four estimations were compared in pairs and the differences between them were evaluated using the Students test ( = 0.05). In general, these differences were revealed to be less and less in the successive calibration cycles (it is seen in Table 5), but it was found that only in the last cycle (i.e. when the standard and sample solutions were diluted to the greatest extent) all estimations were statistically equal to each other. Such an effect was stated in both analyses, i.e.

when the standard solution of both 4.0 and 6.0 mg L1 was used. As four estimations of the analytical result should be theoretically equal to each other, the question is, what could be the reason of signicant differences between some of them. Certainly, the answer should be related to chemical interferences. It is evident, that some components of the cabbage sample (such as aluminium, vanadium, strontium, phosphate anions) could be present in content great enough to act as interferents during determination of calcium. These interferences were reduced (as expected) with the sample dilution and, consequently, the analytical result was be estimated by values cx1 cx4 more and more accurately. Assuming such an interpretation of the effects observed during calibration by the integrated dilution method, the average value of the estimations being statistically equal to each other (i.e. obtained in fth calibration cycle; see Table 5) can be considered as the analytical result found. As seen in Table 5, calcium concentrations found in the concentrated sample were of good precision, which was, however, decreasing with the sample dilution. The reason was that particular estimations were calculated on the basis of signals of increased random uctuations. As a consequence the reliability of the nal analytical result is quite poor in terms of precision. However, this is general disadvantage of the dilution method [58], independent of an instrumental tool and particular procedure using for realization of this method. The results obtained by the integrated dilution method for the sample of a given dilution degree were comparable in terms of precision with those obtained by the interpolative conventional method (see Table 5). However, the conventional approach offers a single analytical result only, hence it was not able in contrast to the integrated method to verify its accuracy. It is the reason, that calcium was determined with quite serious systematic errors, especially when the concentrated sample was analyzed. Above examinations revealed that the manifold designed can be effectively used for calibration by the dilution method

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13

in the integrated mode. It is capable of working properly in terms of the effects expected (as described above) and reproducibly in terms of the results obtained (compare in Table 5 the corresponding results obtained with the use of both standard solutions in successive calibration cycles). There are no any reasons in fact to doubt that it could not be similarly effective when adapted to realization of other calibration approaches mentioned previously. Certainly, a drawback of using the calibration ow system used is relatively long time needed to perform a single calibration procedure. It concerns especially the calibration by the integrated mode, as in such a case the standard and sample zones are required to have the volumes great enough to measure all of analytical signals in the steady-state form. Some methodological and instrumental ideas how to improve the manifold in this respect (but preserving its principle and advantages) are currently tested.

6.

Conclusions

The manifold described and used in this paper is dedicated to realize different calibration methods in various modes. It can serve as a diagnostic tool allowing the analytical system assayed to be checked in simple and fast way (performing calibration in a single cycle) in terms of interferences suspected. It is also capable of realizing calibration procedures in any more sophisticated form, including preparation of required number of standard solutions and dilution of a sample to chosen extent. Specic facility of the manifold is the possibility of diluting the standard and sample solutions simultaneously, giving a chance to calibrate effectively by the dilution method (as shown above). It should be emphasized that the manifold is the calibration module, which can be incorporated to the ow systems of various congurations and analytical purposes. In particular, there are no obstacles to use it in such cases, when a sample is required to be pre-treated before measurements (by means of, e.g. digestion, dilution, reagent addition and separation) as well as when some special ow injection techniques (e.g. merging zone or stopped-ow techniques) are needed to be applied. For instance, in case of calibration by the indirect and internal standard methods is not necessary to add the adequate reagents to the standard, sample and carrier reservoirs (as suggested in Table 4), but they can be introduced to loop L3 of the system (see Fig. 1) through the separate tube in order to be mixed with the standard and sample zones just before detection. It is also evident, that the manifold can be coupled with various detection systems. The manifold designed seems to meet the requirements, which are expected of a calibration system to be applicable to

routine analysis. In particular, it is straightforward in terms of instrumental construction and operation and it allows each calibration procedure to be conceptually easy and clear at all stages (preparation of the calibration solutions, measuring, interpretation of the measurement data and calculation of the analytical results). Moreover, it can be fully computerised and automated. Few years ago it has been reported [1]: When reviewing the FIA literature many interesting and really ingenious concepts can be found concerning how analytical calibration can be performed. No wonder, as FIA has features that are very useful for this purpose. However, in many cases authors apparently pay more attention to FIAs ingenious rather than practical aspects. [. . .] The general impression is that FIA calibration designs are too often developed as a kind of toy rather than as a tool which can serve effectively and reliably in analytical practice. We believe that the calibration manifold presented in this paper can be considered as such a tool being useful enough to be introduced to analytical laboratories. If so, it would be additional chance to popularize some calibration approaches, which are not currently used or used only occasionally, and to use them to overcome various analytical problems.

Acknowledgements
The authors wish to thank Ministry of Sciences and Higher Education (Warsaw, Poland) for nancial support (Project No. TO9A 102 27) of the research described in this work.

references

[1] P. Ko scielniak, Anal. Chim. Acta 438 (2001) 323. [2] P. Ko scielniak, in: J. Niemie snik, W. Chrzanowski (Eds.), New Horizons and Challenges in Environmental Analysis and Monitoring, Centre of Excellence in Environmental Analysis and Monitoring, Gdansk, 2003, p. 110. [3] B. Welz, M. Sperling, Atomic Absorption Spectrometry, third ed., Wiley-VCH, Weinheim, 1999, pp. 534535. [4] T. Takada, K. Nakano, Spectrochim. Acta 36 (1981) 735. [5] S. Fan, Z. Fang, Anal. Chim. Acta 241 (1990) 15. [6] M. Sperling, Z. Fang, B. Welz, Anal. Chem. 63 (1991) 151. [7] L. Pszonicki, W. Skwara, Talanta 36 (1989) 1265. [8] P. Ko scielniak, J. Kozak, Anal. Chim. Acta 460 (2002) 235. [9] P. Ko scielniak, J. Kozak, M. Herman, Instrum. Sci. Technol. 30 (2002) 251. [10] P. Ko scielniak, G. Akcin, M. Herman, J. Kozak, M. Wieczorek, Ann. Chim. 903 (2003) 1045. [11] P. Ko scielniak, J. Kozak, M. Herman, M. Wieczorek, A. Fudalik, Anal. Lett. 37 (2004) 1233.