Accred Qual Assur (2007) 12:295302 DOI 10.

1007/s00769-006-0248-z

G E N E RA L P A P E R

Dry mass determination: what role does it play in combined measurement uncertainty?
A case study using IAEA 392 and IAEA 413 algae reference materials
E. Zeiller E. Benetka M. Koller R. Schorn

Received: 12 September 2006 / Accepted: 19 December 2006 / Published online: 9 February 2007 Springer-Verlag 2007

Abstract Elemental mass fractions are normally reported on a dry-mass basis. In addition, producers of reference material state their property values for dry masses and relate them to a dened dry mass determination method. This paper describes how biases and uncertainties in dry mass correction factors may affect values reported as concentration per dry mass. The inuence of the use of different drying methods, accuracy of drying temperature, length of drying, environmental humidity, and the sample mass used for dry mass determination have been evaluated using two candidate International Atomic Energy Agency reference materials. Deviation from proposed drying methods was observed to lead to differences of up to 5% in dry mass correction factors. In addition, the heterogeneity of sample moisture as well as hygroscopic behaviour during weighing play an important role in the uncertainty estimation. Proposals are made regarding which sources of uncertainty arising from dry mass determination should be considered and included in the combined uncertainty of analytical results. Keywords Reference material Uncertainty dry mass Standard uncertainty Dry mass determination

Introduction The water content of reference materials (RMs) plays an important role in RM production and certication. Producers tend to focus on drying samples as much as possible to avoid instability due to microbiological, enzymatical and/or chemical activities inuenced by the water content of the RM [13]. Complicated handling and bottling procedures need to be applied, requiring controlled atmospheres with low water content [1, 4] or inert conditions such as dry N2 or Ar atmosphere [24] for processing of RMs. On the other hand, dry powders may also cause problems during weighing due to static electricity and hygroscopy [5] and can thus form an additional component contributing to weighing uncertel tainty. Que and Vassileva reported an example where 59.4% of their total measurement uncertainty was related to the hygroscopic behaviour of the sample [6]. Nowadays, other factors are also considered to be important for RM stability. A knowledge of sorption kinetics, moisture equilibrium, energy interaction between water and surface of RMs, the inuence of water activity levels and BET (Brunnauer-Emmett-Teller) water monolayers are becoming increasingly important for RM production and use [710]. For storage stability, water activity levels (the ratio of water vapour pressure over the sample divided by the water vapour pressure of pure water) should be around 0.20.4. The idea is that polar groups on the surface are saturated with water to protect against degradation, e.g. lipid auto-oxidation [10]. The RM group of the International Atomic Energy Agency (IAEA) Seibersdorf Laboratories follows a different approach to production and storage of trace element and radionuclide RMs: materials are allowed

E. Zeiller (&) R. Schorn Chemistry Unit, PCI Agencys Laboratories Seibersdorf, International Atomic Energy Agency, Wagramer Strae 5, 1400 Vienna, Austria e-mail: Elisabeth.Zeiller@IAEA.org E. Benetka M. Koller Austrian Research Centre Seibersdorf, Abteilung Chemie, 2444 Seibersdorf, Austria

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to exist in equilibrium with environmental humidity during processing and bottling, and are then gamma irradiated to improve shelf life. The algal RMs IAEA 392 and IAEA 413 were sterilised twice using a 60Co source directly after collection, and again after reprocessing and nal bottling (in 1997). Evaluation of available long-term data for the new IAEA 392 algae RM [11] conrms the suitability of this approach for the certied elements. Also for other IAEA RMs, no changes in trace element and radionuclide property values due to degradation effects were reported, even after several years of storage. It should be remembered that this approach is not generally applicable, e.g. it cannot be applied when a chemical reaction between moisture and the analyte takes place that leads to a change of identity of the analyte. The contribution of the uncertainty due to instability of analytes is commonly included in the combined standard uncertainty of a property value, as required by ISO 35 [12]. The additional uncertainty contribution of the dry mass correction factor is rarely specically evaluated by RM producers since it is normally covered by the design of the certication study. However, it may play a role for the user of RMs when calculating the standard uncertainty of the RM results. Most publications on this subject deal with comparing differences in dry masses obtained by different drying methods or commercial moisture analysers [6, 9, 10, 13, 14]. Mass losses may relate not only to waterother volatile substances may also be removed. In addition, the different binding forms of water may play a role as well as absorbed water retained on the surface of the solids, the amount thereof being related to humidity, temperature and surface structure. The presence of essential water as an integral part of the molecular or crystal structure [15] must also be considered. A clear denition of the terms water content, moisture content and dry mass is needed for each RM. Although the Karl Fischer method is the commonly accepted method for determination of total water content independent of its binding form [16], this method is not universally available in all laboratories. The RM group of the IAEA Seibersdorf Laboratories decided to evaluate other, more widely available, methods for the dry mass determination of their new Algae RMs. Since the dry mass cannot be as clearly dened as e.g., the water content as measured by Karl Fischer method, in this paper dry mass should be viewed as a good approximation of the true dry mass. The proposed method, which must have good repeatability, should also focus mainly on the absorbed water/ moisture and should not lead to deterioration of the crystal structure of the material. The term moisture is

used in this paper since most dry mass determination methods do not determine the total water content in the samples tested. Investigations have been carried out by the RM group of the IAEA Seibersdorf Laboratories to identify and assess the sources of uncertainty contributing to the determination of the moisture content and the related dry mass correction factor. Methods, sample properties and related environmental factors are considered, and the inuence of the dry mass factor uncertainty on the result uncertainty is shown. This assessment also aimed to provide recommendations for an optimal procedure for moisture content determination, as well as to minimise the related contribution of uncertainty in the practical use of new RMs. Materials and methods Materials Two new IAEA algal RMs were used (IAEA 392, and IAEA 413). Both are naturally grown algae. IAEA 413 was grown on a nutrient solution deliberately contaminated with toxic elements [17]. The moisture content of the samples depends on the ambient humidity and has reported to be in the range of 911% of the sample mass. Experimental procedures Four series of tests were performed: Inuence of drying procedures The inuence of drying procedures and duration of drying for the determination of moisture and mass loss. This was tested in triplicate subsampling using a few commonly used methods: Oven drying (using Duran weighing vessels) was performed at 80 C and 105 C under atmospheric pressure. The temperature deviation was controlled not to exceed 2 C. Mass losses were determined after 2, 4, 6 h and then less frequently until 48 h. Freeze drying was performed in a Modulyo freeze drying system (Edwards, Absolute-Vacuum, Crawley, UK) at 50 C, and 7 mbar pressure. Mass losses were determined after 6, 24, 48, 60 and 72 h. The nal weighings were performed after 144 h. Drying using magnesium perchlorat [Mg(ClO4)2] was performed in a desiccator using fresh, waterfree salt. No vacuum was applied. Karl Fischer water determination

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The Karl Fischer titration was performed with a DL31 Titrator (Mettler Toledo, Greifensee, Switzerland). The method is based on the oxidation of sulfur dioxide by iodine in a methanolic hydroxide solution in the presence of water. In principle, the following chemical reaction takes place: H2 O + I2 + SO2 + CH3 OH + 3RN ! [RNH]SO4 CH3 + 2[RNH]I The titration was performed volumetrically. In this method, a Karl Fischer solution containing iodine is added until the rst trace of excess iodine is present. The amount of iodine converted is determined by reading the burette volume change. The water content of the Karl Fischer agent was determined by titration of ve aliquots of a di-sodium-dihydrate standard with known water content. Experiments were always started simultaneously after shaking the sample bottle for 3 min to rehomogenise segregated sample fractions and to achieve comparable wet masses. Commonly, 0.7 0.2 g was taken for the tests, except for the Karl Fischer water test in which 0.060.1 g was used. A calibrated analytical balance reading to 0.1 mg accuracy was used to weigh samples. Inuence of sample heterogeneity The inuence of sample heterogeneity on dry mass determination was evaluated by examining repeatability of experiments. For all tests, an in-house protocol for dry mass determination was followed (4 h, 80 C, covering the weighing container during the transfer and cooling period to reduce the inuence of environmental humidity) [18]. Some existing dry mass data from the certication process were also used. The following factors were tested: Within-bottle homogeneity (23 sub-samples per bottle per test) Between-bottle homogeneity (1 sub-sample per 23 bottles per test) Long-term effects (66 and 75 sub-samples from several bottles) Inuence of mass (2 sub-samples per mass using 1 bottle per RM). Dry mass was determined from original bottles or bottles stored in a refrigerator after opening; this provided insight into long-term effects. With the exception of the long term tests, the value obtained for moisture content after drying for 4 h at 80 C was used to nor-

malise the results, making them independent of environmental humidity. Inuence of environmental humidity The inuence of environmental humidity was monitored. Mass changes, i.e. decrease in test-sample mass due to dry environmental conditions or increase in test sample mass due to high humidity, were determined. Three sub-samples of 1 g were stored: in a desiccator lled with water (9398% humidity) in the laboratory environment (2330% humidity) in a desiccator lled with dry silica gel in a balance compartment with increasing relative humidity (2550%).

For the latter test the results of only one sub-sample are reported since it was not possible to obtain reproducible conditions for the moisture in the balance (the moisture was increased simply by placing some water containers in the balance compartment and recording hygrometer values). The room temperature was kept within 23 1 C. Mass changes were recorded at regular intervals, and used to derive the amount of water absorbed. Inuence of small temperature changes The inuence of small temperature changes in the drying equipment on dry mass was also tested. To this end, a 4 h drying at 80 C served as a reference approach for these algal RMs. Since most ovens used for drying are not equipped with calibrated thermometers, small deviations from recommended temperatures may easily occur. The temperature in the oven used in these experiments was veried with a calibrated thermometer. Duplicate drying tests were performed at 75, 80 and 85 2 C, the temperature values being recorded based on reading of the calibrated thermometer. For this test, one bottle per RM was used and all test samples were weighed at the same time. The drying containers were covered and stored until the temperature conditions in the drying equipment fullled the test requirements.

Results and discussion Inuence of drying procedures As in many other publications on this topic [6, 9, 14, 19, 20], the Karl Fischer method was used as a reference

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method to dene the true water content. The shaded areas in Figs. 1 and 2 show the repeatability standard deviation obtained using this method. The dry mass results obtained with other methods were compared to these reference values. Both algal samples showed similar trends using the applied drying procedures (Figs. 1, 2). Freeze drying and oven drying for 4 h at 80 C gave results closest to Karl Fischer test results. Mg(ClO4)2 drying, even after 600 h, could not result in dry mass values comparable to the Karl Fischer data. Obviously, 600 h drying is also not very practical for routine use. Oven drying at 105 C gave results that were lower than those obtained with all other methods. Even for short drying times (26 h), the dry mass factor of IAEA 392 barely overlapped the larger standard

deviation (about 0.7% RSD) of the Karl Fischer test result. For IAEA 413 the difference in the dry mass between oven drying and Karl Fischer was as much as 1.5%. This trend would have been even larger if drying until constant weight had been applied. For IAEA 392 the relatively higher standard deviation obtained using the Karl Fischer method may be due to the fact that smaller sample masses were used (about 0.06 g). Drying tests at 80 C showed that the repeatability standard deviation increases if smaller sample masses are used (Fig. 3). This effect cannot be explained by weighing uncertainty but it may be attributed to, e.g. sample heterogeneity or the hygroscopic behaviour of the algal material. Similar observations have been made in the past for leaves and other environmental samples [13]. Inuence of sample heterogeneity

94 94 93 93 Dry mass [%] 92 92 91 91 90 90 89 0 20 40 60 Time [h] 80 100 120

x Mg (ClO4)2
Freeze drying 80 C 105 C

Karl Fischer RSD

Fig. 1 Relative dry masses obtained for IAEA 392 reference material using different drying methods compared to that obtained using the Karl Fischer method

94 93 92 Dry mass [%]

An impression of the variability resulting from sample heterogeneity as related to moisture content can be obtained from Table 1, which shows data from dry mass determinations. Although the individual tests were performed on the same day under the same conditions, within-bottle and between-bottle variability indicate that the amount of moisture is not the same in the various bottles. The difference between multiple determinations within one bottle was very small, and was less than the difference between bottles. Higher between-bottle differences can be explained by slightly different humidity conditions on the days of bottling. The long-term (7 years) average value comprises the inuence of environmental humidity during storage and sample weighing in addition to heterogeneity variation. No signicant differences were found between the moisture fractions of freshly opened bottles and fractions determined in the past upon rst preparation of the materials; nor were differences found in

0.4

91
Karl Fischer RSD

0.35 0.3

90

RSD [%]
120

0.25 0.2 0.15 0.1 0.05

89 88 87 0 20 40 60 Time [h] 80

x Mg (Cl4)2

Freeze drying 80 C 105 C

100

0 0 0.1 0.2 0.3 0.4 0.5 0.6 Mass [g] 0.7 0.8 0.9 1

Fig. 2 Relative dry masses obtained for IAEA 413 candidate RM using different drying methods compared to that obtained using the Karl Fischer method

Fig. 3 Inuence of sample mass on the relative standard deviation [RSD%] of within-bottle dry masses of IAEA 392

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Accred Qual Assur (2007) 12:295302 Table 1 Minimum, maximum and mean relative standard deviations (RSD%) calculated from dry mass determination results in IAEA 392 and IAEA 413 Algae reference materials Mass fraction dry% In-bottle IAEA 392 Between-bottle IAEA 392 Long-term IAEA 392 In-bottle IAEA 413 Between-bottle IAEA 413 Long-term IAEA 413
a

299

No. RSD% RSD% RSD% of min max meana tests 8 8 66 0.02 0.08 0.20 0.89 0.09 0.38 0.73 0.02 0.37 0.12 0.86 0.06 0.66 1.12

From 88.5 to 93.0

humidity. The water absorption effect was very rapid in the rst few minutes and slowed down after about 2 h to give nal values of about 34%. Since both algal materials are hygroscopic and were bottled at low humidity (about 3035%), the effect due to elevated environmental humidity is more signicant than the moisture loss due to low environmental humidity (Fig. 5). For low environmental humidity, the decrease in mass is less than 1.5% within the rst 7 h. This hygroscopic behaviour is important especially when weighing small amounts of sample. Inuence of small temperature changes Differences between the actual temperature, derived from the calibrated thermometer, and the reading obtained from the oven thermometer may be in the order of 5 C. These small temperature changes can cause differences of up to 0.8% in the dry mass determination, compared to data sets from oven drying at 80 C (Fig. 6). The t-tests performed with data from both materials (assuming unequal variances, 95% con-

From 89.9 to 92.2

8 6 75

For long-term data, only the mean standard deviation of all tests is reported

Sample mass [%]

fractions determined after bottles had been opened and stored at 4 C in a refrigerator for further use. Algal RMs IAEA 392 and IAEA 413 showed dry masses of between 89.9 and 92.2% and between 88.5 and 93.0%, respectively, of the total sample masses used for the determinations. In both materials the overall relative standard deviation (RSD) of long-term experimental data was good (<1.12%), but the differences of several percent between the highest and the lowest dry mass values indicate the need for repetitive determinations each time the RMs are utilised. Inuence of environmental humidity Figure 4 shows the increase in mass due to water absorption. For an environmental humidity of about 50%, the mass increases were between 0.2 and 0.4% within 2 min for samples having been stored at 2330%
1.8 1.6

130 125 120 115 110 105 100 95 0 10 20 30 40 Time [h] 50 60 70 80

IAEA 413 98% IAEA 413 10% IAEA 413 25% IAEA 392 98% IAEA 392 10% IAEA 392 25%

Fig. 5 Mass changes in 1 g samples (trend lines) for samples stored at 10, 25 and 98% relative humidity. RSD (n = 3) was <0.3% for all points

Mass increase [%]

1.4 1.2 1 0.8 0.6 0.4 0.2 0 0

IAEA 392 IAEA 413

Dry mass [%]

92.40 92.20 92.00 91.80 91.60 91.40 91.20 91.00 90.80 IAEA 392 IAEA 413

10

12

70

75

80
Temperature [C]

85

90

Time [min]

Fig. 4 Mass increase due to water absorption after transfer of 1 g sample from 25% humidity to 50% environmental humidity

Fig. 6 Inuence of small temperature changes on dry mass (%) results in duplicate measurements

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Accred Qual Assur (2007) 12:295302 Table 2 Inuence of different drying methods and corresponding dry mass correction factors on the mass fraction (Cs) and its combined uncertainty (uCs). The experimentally evaluated ufdm was 0.82% (k = 1) Element Drying method fdm ufdm applied Pb Pb Co Co 80 C, 4 h 105 C, 24 h 80 C, 4 h 105 C, 24 h 0.914 0.899 0.914 0.899 Cs uCs mg/kg dry

dence) showed that the differences in dry masses were signicant, and higher than could be assumed from the within-bottle repeatability experiments. Contribution to the combined standard uncertainty: some examples for consideration Limiting the uncertainty of the dry mass factor only to the contribution from weighing is too simplistic. Figure 7 shows the area of the cause-effect diagram related to the dry mass correction factor that will inuence the combined standard uncertainty. Balancerelated components (sensitivity, linearity, Buoyancy correction) were not considered in the above examples because the same balance was used and a ratio was determined. The mutual interaction of the other components can be complicated and may differ for different types of sample. Experimental results and expert judgment should be applied for the evaluation and combining of the uncertainty components; in most cases the use of the law of propagation would lead to overestimation of the total standard uncertainty of the dry mass factor. In particular, hygroscopicity and method-related aspects might increase the uncertainty of the dry mass correction factor considerably as can be seen for the algal materials. Table 2 shows ICP-OES results calculated for IAEA 413 during the certication process and the combined standard uncertainties with two different drying methods. Assuming a realistically high uncertainty for the dry mass correction factor (experimental data obtained during the certication measurements were used, ufdm = 0.82%) the analysis results still have overlapping combined uncertainties, but for the Pb

0.007 233.69 3.53 (1.51%) 0.007 237.56 3.61 (1.52%) 0.007 4.15 0.31 (7.45%) 0.007 4.21 0.31 (7.45%)

example, the difference between the results already equals the total analysis uncertainty assigned to these results. The magnitude of the dry mass uncertainty on the combined uncertainty can be further illustrated by the example shown in Table 3. This table shows ICP-OES results and their combined standard uncertainties for a range of elements analysed in IAEA 413. The following formula was applied to calculate the elemental content in dry algae. Cs css cbl V frec fdrift fint fdm m 1

The uncertainty of the dry mass fraction, Cs (mg/kg), was a function of the uncertainties of concentration of the sample (css) and blank (cbl) solutions (covering the calibration and calibration standards uncertainties), and the sample wet mass (m) and the volume (V) of the sample solution. The uncertainties of the correction factors for instrument drifts (fdrift), and dry mass (fdm) ratio dry/wet mass were also considered. For calculation of the combined standard uncertainty of the measurement, the spreadsheet method

Fig. 7 Causeeffect diagram branch related to dry mass factor uncertainty

Balance Environmental Heterogeneity conditions/storage Mass Balance Drying Method Other method specific factors Binding form of water

Time Temperature

Mass wet

Mass dry
Surface/mass Environmental conditions Volatile substances Hygroscopicity Surface/mass Environmental conditions

Hygroscopicity

dry mass factor

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Table 3 Relative contribution of the uncertainty of the dry mass factor (ufdm = 0.82%) to the combined uncertainty of the ICP-OES measurements for IAEA 413 Element Mass fraction (mg/kg) uCs (mg/kg) uCs % k=1 Relative contribution (%) to the standard uncertainty (uCs) of the elemental dry mass fraction uCss Cd, 226.502 nm Pb, 220.353 nm Ni, 221.647 nm Cr, 267.716 nm Zn, 206.200 nm As, 193.695 nm Co, 228.616 nm 199.73 233.69 111.37 377.13 163.86 126.30 4.15 2.90 3.53 1.93 7.10 3.52 5.77 0.31 1.45 1.51 1.74 1.88 2.15 4.57 7.45 34.15 32.71 44.26 22.78 18.03 18.10 30.77 uCbl 0.36 36.50 4.36 0.03 0.50 74.53 58.18 uV 0.02 0.02 0.02 0.01 0.01 0.00 0.00 Um 0.03 0.03 0.02 0.02 0.02 0.00 0.00 ufdm 32.04 28.99 22.17 18.84 14.48 3.24 1.21 ufdrift 33.38 1.75 29.16 58.31 66.96 4.12 9.84

was applied [21] using the above formula. Uncertainties for interference (fint) and recovery (frec) factors, although possibly being equally important for the total standard uncertainty of the measurement, were not included since the experiments did not detect reasons to adjust results (clear solutions, equal results for different wavelengths and dissolution techniques etc.), and uncertainties related to interferences and recoveries are covered during the certication process by combining data from different methods and laboratories. A double counting of recovery uncertainties was avoided as proposed in the Guidelines for the use of recovery factors [22] since the uncertainty of the recovery is already included in the estimates of precision and between-laboratory bias. Table 3 shows the relative contribution of the dry mass correction factor uncertainty of 0.007 (ufdm = 0.82%) to the total uncertainty of ICP-OES measurements performed for the certication of IAEA 413. It can be seen that even this small dry mass factor uncertainty may contribute up to 32% to the combined standard uncertainty. In general, this inuence can be said to decrease with increasing total uncertainties. Summary Correction of the sample dry mass for moisture may play an important role when using RMs. The results presented in this paper conrm that the uncertainty components related to dry mass correction should not be neglected and may even, under certain conditions, make the most signicant contribution to the combined standard uncertainty. The use of a different drying method may lead to biases of several percent depending on the method used and the type of sample, and even small temperature changes in the drying oven can lead to biases. The hygroscopic behaviour of the sample material should be considered by the user, and the sample mass used for dry mass factor determina-

tion should be high enough to be representative for that RM. Differences in dry mass determination may be one of the sources of incomparability of results, and it should be emphasised that RM producers and PT organisers should determine the optimal dry mass determination method before sample characterization to assure that no additional biases are included in the certication uncertainty. Possible sources of uncertainty of the dry mass correction factor should be experimentally determined and this information should be made available to the user. The critical parameters of a proposed dry mass determination method are different for different sample matrixes, and knowledge of these parameters (e.g. hygroscopic behaviour, moisture homogeneity at low sample masses) can help the RM user to reduce dry mass factor uncertainty. In addition, the selected dry mass determination method should be available in most laboratories of expected RM users. Although Karl Fischer provides a well-dened determination method of the total water content, its worldwide availability cannot be assumed. In conclusion, the RM group of the IAEA Seibersdorf Laboratories has decided to select oven drying for 4 h at 80 C as the recommended procedure for algae RMs IAEA 392 and IAEA 413. This method, as well as freeze-drying, gives overlapping dry mass results with the Karl Fischer method. Oven drying is easy to perform, and is usually available in most laboratories. Taking into account the results of the experiments performed here, an uncertainty contribution of 0.51% for the dry mass correction seems to be realistic for these two algae RMs if the proposed dry mass determination method is used. This estimate can further be reduced if: sample mass is more than 500 mg (preferably 700 mg) drying temperature is well controlled heterogeneity of material is considered when applying a multiple dry mass determination

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Accred Qual Assur (2007) 12:295302 9. Yazgan S, Bernreuther A, Ulberth F, Isengard H-D (2006) Food Chem 96:411417 10. Ruckhold S, Grobecker KH, Isengard H-D (2001) Fresenius J Anal Chem 370:189193 11. Zeiller E, Shakashiro A, IAEA/AL/148 (2005) Report on the characterization of the naturally grown algae reference material IAEA 392 12. ISO Guide 35 Reference materials. General and statistical principles for certication, 3rd edn. 2006 13. Krachler M (2001) Fresenius J Anal Chem 371:944950 14. Vogl J, Ostermann M (2006) Accred Qual Assur 11:356362 15. Dean JA In: Analytical chemistry handbook, McGraw-Hill, New York, ISBN 0-07-016197-6, 1.131.14 16. Karl Fischer (1935) Angew Chem 48:394396 17. Zeisler R, Dekner R, Zeiller E, Doucha J, Mader P, Kucera J (1998) Fresenius J Anal Chem 360:429432 18. IAEA Chemistry Units internal working instruction CUI.GE.004 (revision 2006) 19. Rueckhold S, Grobecker KH, Isengard H-D (2000) Fresenius J Anal Chem 368:522527 20. Schmitt K, Isengard H-D (1998) Fresenius J Anal Chem 360:465469 21. EURACHEM/CITAC Guide (2000) In: Quantifying uncertainty in analytical measurement, 2nd edn. QUAM:2000.P1 22. Thompson M, Ellison SLR, Fajgelj A, Willetts P, Wood R (1999) Pure Appl Chem 71:337348

samples for analysis and for dry mass determination are in equilibrium with environmental humidity before weighing (especially in very humid environments).
Acknowledgments The authors would like to thank Dr. P. Bode (Delft University of Technology), Dr. A. Toervenyi, and Dr. U. Sansone (both IAEA) for fruitful discussions and comments on our paper.

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