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Plant Analysis Procedures
Second Edition

Plant Analysis Procedures
Second Edition

Edited by

Erwin E.J.M. Temminghoff
Wageningen University,
Department of Soil Quality,
The Netherlands

and

Victor J.G. Houba

KLUWER ACADEMIC PUBLISHERS
DORDRECHT / BOSTON / LONDON

101 Philip Drive.O. mechanical. P. recording or otherwise. ISBN 1-4020-2769-9 (HB) ISBN 1-4020-2976-4 (e-book) Published by Kluwer Academic Publishers. MA 02061.S. 3300 AA Dordrecht.O. for exclusive use by the purchaser of the work. or transmitted in any form or by any means.P.A. Box 17. Box 322. 3300 AH Dordrecht. P. with the exception of any material supplied specifically for the purpose of being entered and executed on a computer system. microfilming. Printed in the Netherlands. electronic. sold and distributed by Kluwer Academic Publishers. The Netherlands. without written permission from the Publisher. In all other countries. stored in a retrieval system.I. U.A C. Printed on acid-free paper All Rights Reserved © 2004 Kluwer Academic Publishers No part of this work may be reproduced. Central and South America by Kluwer Academic Publishers. Catalogue record for this book is available from the Library of Congress. photocopying. Norwell. . Sold and distributed in North. The Netherlands.

The elements are in alphabetic order of symbols. The authors accept no responsibility whatsoever for any harm caused by the application (right or wrong) of these procedures. Peter Nobels for the optimisation information regarding the ICP-OES and Mrs.483766 .(0)317. new digestion techniques were included like microwave. each determination is tailored to the conditions of the digest/extract one is working with. J. Any questions. Thus.G. It has been reorganized and put into a new handsome format.J. course in Soil Science and Water Management and the International Postgraduate Course on Soil and Plant Analysis and Data Handling. Houba. For almost all elements different measure techniques are available. V PREFACE This syllabus is a revised and extended edition of the former "Plant Analysis Manual’ by I. and all corresponding determination procedures are placed in the same chapter.482357 fax: +31. The Manual is arranged according to the methods of digestion and extraction. W.Sc. Gerdine Gaikhorst regarding the ICP-MS. Walinga.O. Also new measure techniques were included like ICP-OES and ICP-MS. With this second edition of the Manual. We hope this Manual is very useful in your laboratory during analysis of all kind of plant materials.J.M.(0)317. Box 8005 6700 EC Wageningen The Netherlands e-mail: erwin. Erwin J.temminghoff@wur.nl tel: +31. suggestions for improvements should be addressed to: Dr. van Vark & I. Temminghoff Wageningen University Department of Soil Quality P. We would like to thank Mr. comments. V. van der Lee. Novozamsky (ISBN 0-7923-3182- 6) originally meant for use within the M.

............. P.........B DETERMINATION OF ALUMINIUM BY ICP-OES................ Ni.............................................. Sn.........................1...........V CONTENTS ............... Sn.. Cd.... 10 For the determination of total Ca.... Mg..... DETERMINATIONS..... Ni............... As....... S.........................H2O2 ....... Sb...1 DETERMINATION OF ALUMINIUM..............H2O2 AND SELENIUM.......... Na...... Pb..............................HF ........................... Cu.. INTRODUCTION ....6 DIGESTION WITH HNO3 ....................................................... Mn........................... 30 For the determination of total B and Si 4..................... 32 4...... Fe........................................... Cd...............1... Ca........................................................................................................................ Pb........................H2O2 ...................... N........................ As. P.. Mn................................ Cr................. For the determination of total B 3.......... Mg..................... 3 1....................................... P..... K...... 32 4........................... Mn............ K..... V and Zn 2...... Sb. Na.......................... Cu...........................HCLO4 ........1 ORGANISATION OF THIS MANUAL.................................. 16 For the determination of total Al.... Co........ Mg.......... N................ Mg... K..............................HF......... 28 For the determination of Cl-....... S............... 1 1.....3 SAMPLING AND PRETREATMENT ................. EXTRACTIONS ....................... 1 1...... V and Zn 2........... 7 2..... Mg. Ca.....................SALICYLIC ACID .........................................3 MICROWAVE DIGESTION WITH HNO3 .... Ni............................. V and Zn 2...........1 DIGESTION IN TUBES WITH H2SO4 ..4 DIGESTION WITH HNO3 ............. Na.. Co.... 19 For the determination of total S 2.................... DIGESTIONS........H2O2 .... Pb................. Cu.... 32 4......................SALICYLIC ACID ................................... 7 For the determination of total Ca.....1 EXTRACTION WITH WATER ...................... Cr............... 24 For the determination of total Al............. 35 .........A DETERMINATION OF ALUMINIUM BY SPECTROPHOTOMETRY ....... Ca................7 DIGESTION BY DRY-ASHING FOLLOWED BY TREATMENT WITH HF ... 28 3............. Cr................................................. Fe....................................................................... N.. Sn..8 DIGESTION BY DRY-ASHING IN THE PRESENCE OF CAO...............5 DIGESTION WITH HNO3 ..............and SO42- 3.... Mn. Na.. K. 5 2.......2 EXTRACTION WITH HF ................................................ 21 For the determination of total Cd.......2 DIGESTION IN FLASKS WITH H2SO4 ..............HCL .................................................. K................. Na............................... Sb.......... 13 For the determination of total Al.............................. As......... NO3............... P and Zn 2..............VII 1........ Fe.......................................2 TECHNICAL REMARKS .............H2SO4 .... and Zn 2................. NO2-. Cu......... Mn........ Cd.. S....... P.......... Fe................................................................. Mn and Zn 2.............................................. Co.......................... VII CONTENTS PREFACE .....

...................…………………………………………………72 4............................ 94 .......8 DETERMINATION OF CHROMIUM................B DETERMINATION OF CHROMIUM BY ICP-MS........................................................C DETERMINATION OF ALUMINIUM BY ICP-MS......... 80 4................................................................................................. 37 4.......... 84 4......................A DETERMINATION OF COBALT BY ICP-OES............................ 82 4...........B DETERMINATION OF IRON BY ICP-OES....................................B DETERMINATION OF COPPER BY ICP-OES....................8.............4 DETERMINATION OF CALCIUM.........5.............................................................................................A DETERMINATION OF CHROMIUM BY ICP-OES ……………………………………………........................ 78 4................................................ 41 4....D DETERMINATION OF CADMIUM BY ICP-MS......A DETERMINATION OF BORON BY SPECTROPHOTOMETRY ..... 68 4....................................10 DETERMINATION OF IRON..........2 DETERMINATION OF ARSENIC....B DETERMINATION OF COBALT BY ICP-MS..5................... 90 4...... 62 4....................................................................................................................................4..11 DETERMINATION OF POTASSIUM...........................................A DETERMINATION OF CALCIUM BY FLAME AES .............4..................................1.................. 39 4.......................................................................................... 72 4................10...........................................................5..................................A DETERMINATION OF CHLORIDE BY COULOMETRIC TITRATION ................................................9......................C DETERMINATION OF COPPER BY ETA-AAS ... 47 4.... 41 4.....................................................................................................................................A DETERMINATION OF CADMIUM BY FLAME AAS ...............................................A DETERMINATION OF ARSENIC BY ICP-MS .......9...........2................ 66 4.. 44 4................................................................................5...............C DETERMINATION OF CALCIUM BY ICP-OES...............................6.................................. 56 4....................................................................A DETERMINATION OF IRON BY FLAME AAS .........D DETERMINATION OF COPPER BY ICP-MS. 50 4...............B DETERMINATION OF CADMIUM BY ICP-OES.................. 47 4................. 68 4.... 88 4...8........... 56 4........................................................3......9.................................5 DETERMINATION OF CADMIUM............9.... 92 4.......................... 76 4.......................................................... 53 4....3 DETERMINATION OF BORON............................................7 DETERMINATION OF COBALT ...............7..............................6 DETERMINATION OF CHLORIDE ......................................76 4.....................................................7....... 39 4..........................3.................................... 80 4...........................VIII Contents 4..........B DETERMINATION OF CALCIUM BY FLAME AAS ................A DETERMINATION OF COPPER BY FLAME AAS .........9 DETERMINATION OF COPPER........ 724 4. 59 4.....10..............................C DETERMINATION OF CADMIUM BY ETA-AAS ........ 90 4.....................4......................B DETERMINATION OF BORON BY ICP-OES................................

........... 157 4....................................... 149 4....B DETERMINATION OF NICKEL BY FLAME AAS ...................A DETERMINATION OF SODIUM BY FLAME AES .............. 153 4...............A DETERMINATION OF TOTAL NITROGEN BY SPECTROPHOTOMETRY ..................19 DETERMINATION OF SULPHUR FRACTIONS............................................................................... 146 4... 128 4............14.......................................E DETERMINATION OF NITRITE BY SFA............. 162 ...................B DETERMINATION OF LEAD BY ICP-OES ...................................................... 113 4.................................................. 102 4.............. 99 4...........C DETERMINATION OF NICKEL BY ICP-MS ....................... 159 4.....C DETERMINATION OF LEAD BY ETA-AAS......18..................................... 159 4............ 142 4.. 94 4.......... 122 4......................................................... 119 4......................B DETERMINATION OF SULPHATE BY ICP-OES................................... 149 4.B DETERMINATION OF TOTAL PHOSPHORUS BY SFA ...............................................................................................B DETERMINATION OF MAGNESIUM BY ICP-OES.......... 104 4......A DETERMINATION OF NICKEL BY FLAME AAS .17...A DETERMINATION OF MAGNESIUM BY FLAME AAS .18 DETERMINATION OF LEAD ....................................................... 131 4.....17.............................11.......................13..................16....................17 DETERMINATION OF PHOSPHORUS ...14.................. 107 4...................13..B DETERMINATION OF SODIUM BY ICP-OES ................................ 133 4.......14...................................................................................14........................................ 116 4..C DETERMINATION OF NITRATE (+ NITRITE) BY SFA..............................................................................B DETERMINATION OF TOTAL NITROGEN BY SFA ...... 135 4................17........16..... 139 4..A DETERMINATION OF POTASSIUM BY FLAME AES .................... 133 4...............................A DETERMINATION OF TOTAL SULPHUR BY ICP-OES .............................. 125 4..............D DETERMINATION OF NITRATE-NITROGEN BY ISE .................15 DETERMINATION OF SODIUM .............................................A DETERMINATION OF LEAD BY FLAME AAS .................C DETERMINATION OF TOTAL PHOSPHORUS BY ICP-OES ...............B DETERMINATION OF MANGANESE BY ICP-OES............................................................16 DETERMINATION OF NICKEL............. 104 4.................................................13 DETERMINATION OF MANGANESE..........................................B DETERMINATION OF POTASSIUM BY ICP-OES.......................... 133 4.............................................12 DETERMINATION OF MAGNESIUM...... 151 4.......................................................18............12.................................................................14 DETERMINATION OF NITROGEN FRACTIONS...........................................................................A DETERMINATION OF MANGANESE BY FLAME AAS ..................................................C DETERMINATION OF MANGANESE BY ICP-MS .....................D DETERMINATION OF LEAD BY ICP-MS.....................18......... 97 4....................................................... 113 4....15... 99 4......................................18.................19..12.................... 139 4......Contents IX 4................................ 128 4.........................19.....11............A DETERMINATION OF TOTAL PHOSPHORUS BY SPECTROPHOTOMETRY ...15................................................................... 110 4.16.........................14.....13...

...................A DETERMINATION OF ZINC BY FLAME AAS ......................................23......................................................................24..........................21 DETERMINATION OF SILICON .........................................................................................................................................24 DETERMINATION OF ZINC ...... 174 4...... 172 4... 167 4..............A DETERMINATION OF SILICON BY ICP-OES ...................................... 170 4..... 178 ..... 167 4.....................B DETERMINATION OF ZINC BY ICP-OES ...............................A DETERMINATION OF VANADIUM BY ICP-MS .................................................20 DETERMINATION OF ANTIMONY................................................................................................................................22...A DETERMINATION OF TIN BY ICP-MS .... 165 4.24......................20..................................24................................21................................... 176 4................ 172 4......................C DETERMINATION OF ZINC BY ICP-MS....................... 165 4............. 174 4.................................................................A DETERMINATION OF ANTIMONY BY ICP-MS ................ 170 4........................X Contents 4.....................23 DETERMINATION OF VANADIUM..................................................22 DETERMINATION OF TIN ......................

In the field of plant analysis there is a confusing variety of methods and procedures. 1 1. In many cases. a separate digestion using larger quantities of plant material is sometimes needed for trace elements in order to obtain measurable concentrations. which is handed in for analysis. however. INTRODUCTION 1. the following methods are applied: flame atomic emission spectrometry (flame AES). It is assumed that every analyst and laboratory technician realises that all chemicals are unsafe. In those cases. Exceptions are . both for digestions and determinations. After ample discussion. It is anyhow assumed that the material. however. potentiometry (ion selective electrodes (ISE)) and coulometry will be encountered.3. This may be the first article on the subject in question. Often. regardless of the chemical structure in which it occurs in the plant. compiled in section 1. since it is very inconvenient to be forced to riffle through the pages while performing the analysis. the present manual only contains ready-to-hand procedures without any comment. Depending on the kind of element and the expected concentration level. For example. no warnings are given with respect to safety. all extraction procedures in one chapter and all determination procedures in one chapter. Therefore. in many cases the digestion and the subsequent determination are interrelated. In principle. more than one method is described to determine a component. Sampling and conservation of plant material are beyond the scope of this manual. Many of the methods in this manual have been checked in our laboratory. we have chosen for a design in which all digestion procedures are described in one chapter.1 ORGANISATION OF THIS MANUAL This manual is intended for the practising chemist who has to do a job in analysing plant material. electrothermal atomisation (graphite furnace) atomic absorption spectrometry (ETA-AAS). As a consequence. this has been indicated within each individual determination procedure. Literature references are only sparingly mentioned. each procedure is fully written down. Most procedures are designed to give a total content value of the element under consideration. but it may also be a recent (review) paper as well. one and the same determination procedure can be applied to different digests. inductively coupled plasma mass spectrometry (ICP-MS). which frequently occur in the plant. inductively coupled plasma optical emission spectrometry (ICP-OES). mainly spectrometric techniques are used here. as well as an alternative in case of instrumental or analytical problems. in principle only if these provide specific extra information. without reference to likewise procedures. For determination of the elements. This provides a reference. In general. moreover. one has to choose a suitable digestion method in combination with the intended determination technique. Besides. flame atomic absorption spectrometry (flame AAS). which is reflected by specific remarks. some general remarks are. one procedure is described with special reference to the different media. is representative for the purpose of the principal. although to a different extent. The procedures described are only for inorganic components. The standard series should then be made with different acids so as to match the acid type and strength of the sample digests in question. spectrophotometry and segmented flow analysis (SFA).

however. even in small amounts. There is very much literature on the subject of laboratory safety. that the waste from a laboratory might be very detrimental for the environment. For the rest it is assumed that all pipetting is done with the help of pipette fillers. that safety goggles are worn when performing digestions. Users are strongly recommended to take appropriate measures in order to minimise these effects. it is strongly recommended to consult such safety manuals and to observe the safety rules given therein. etc.g. KCN. . No special references are made with respect to the impact of these procedures on the environment. e. that work is done in a fume hood when harmful fumes may be released.2 Introduction. Organisation of this manual only made in the case of a particularly toxic or harmful substance. The user should realise.

a sentence may read "dissolve 2 g in 50 mL" when this is the normal amount for one run. it will be mentioned explicitly. By making use of a High Resolution ICP-MS less interferences are expected. however.) is supposed to be available. For clarity and brevity. the classical volumetric pipette can be substituted by plunger-type pipettes or by dispensers. these are summarised below. and bismuth are used as an internal standard mixture. With automated methods. 10 g in 250 mL. • All reagents are assumed to be of analytical grade. all reagents are given per litre. rhodium (amu 103). and bismuth (amu 209) will be nebulised in the plasma together with the sample. so that there is no need to repeat them with every procedure. . since the consumption simply depends on the number of determinations. You may prepare. calibration of pipettes is needed. that a negligible acid concentration exists by preparation between the standard series individually and the samples. Differences in element concentrations in the plant digests can affect the nebuliser and/or the plasma conditions. • In the case of ICP-OES measurements scandium and/or beryllium is used as an internal standard. • Procedures are pointed at consumption of minimum amounts of reagents. glassware or plastic ware is needed. 3 1. or any multiple. germanium (amu 72). Therefore a mixture of scandium (amu 45). either demineralised (demi-) or ultra pure water (UPW) is meant. Ultra pure water is necessary when sensitive measuring techniques like ETA-AAS or ICP-MS will be used to measure very low concentrations. The acid concentration should be that low. • In the case the concentrations in plant digests are to low for flame AAS or ICP-OES one should use ETA-AAS or ICP-MS. however. For work where high precision is required. By measuring also scandium or beryllium a correction can made for all measured elements since the measured scandium or beryllium concentration should be constant. agreements and conventions. Thus. • The common simple laboratory equipment and glassware (hot plates. beakers etc. provided that these are regularly calibrated. rhodium. • In the author’s laboratory an ICP quadropole mass spectrometer is used. unless otherwise indicated. • Standard solutions with concentrations below 1 mg/L should be prepared in diluted acid to prevent adsorption of the standard by glass. • It is assumed that all glassware has been cleaned thoroughly. germanium. Differences in element concentrations in the plant digests can affect the nebuliser and/or the plasma conditions. • In many cases. The element within the internal standard mixtuere which has to be used for correction is the one which is close to the mass of the element of interest.2 TECHNICAL REMARKS In applying the procedures described in this manual. Therefore scandium and/or beryllium will be nebulised in the plasma together with the sample. • In the case of ICP-MS measurements scandium. if you intend to do more runs. If special equipment. one should realise that there is a number of underlying assumptions. • When water is used. This is in particular convenient for dispensing concentrated acids.

and mg/kg or µg/kg for microelements. • The atomic weights used for calculation are the most recent available. thus. 2. Within this system there is a preference for the use of basic units. anyone can set up his/her own way of calculating. For this manual we have chosen to adhere to the generally accepted usage of mmol/kg and mg/kg for macro elements. • The reproducibility of determinations by the given procedures is given by a coefficient of variation (%).e. . a condensed formula is given. the use of volumetric flasks is explicitly prescribed for stock solutions. We have also chosen for the consequent use of molarity in stead of normality. • SI units have been used throughout this manual. i. e. By applying this convention. • For calculation of the results. At low contents however a constant variation can be found therefore in many cases the reproducibility is given as a variation coefficient (%) + a constant value.. Pure Appl. IUPAC commission on Atomic Weights and Isotopic Abundances: Atomic Weights of the Elements 1987. In practice. GLP). In this way. there is no need to prescribe the required glassware. As exception to the rule. the density of water should be given in kg m-3. Chem. L. 1998. that any laboratory should take measures to improve and maintain the quality of its analytical results (Good Laboratory Practice. we have chosen for the use of g/mL if this does not cause ambiguity. however. (1988) 60: 841-854. In particular. whereas the final result can be checked by the given formula. Thus. Guidelines for quality management in soil and plant laboratories. . 1998). • It may be mentioned here. so that these may be used even though their intrinsic precision is not needed.g. so that the user can select appropriate equipment according to his own findings. volumetric flasks are very convenient to handle. • The content of a compound in plant material can be expressed in (milli)moles or (milli)grams per kg. IUPAC (1987). Rome 0-144.4 • The number of significant digits is an indication of the required precision. 1000 mL is far more precise than 1 litre. For better readability. the use of certified reference and reference samples (Quality Control Charts) and an active membership of inter-laboratory trials (ringtests) are appropriate means for this purpose (Van Reeuwijk. ISDN 92-5-104065-6. FAO Soils Bulletin 74. REFERENCES 1.P. for mixing. Van Reeuwijk.

fruit). since the chemical composition may vary strongly. Agricultural University. which means dried at 105 oC. 0. Sci.J. The plant sample is normally dried at 70 oC in a well-ventilated drying oven till dry (often within 24 hours).G. Commun. that a mill might contaminate the sample with Al. in order to obtain a homogeneous sample from which representative sub-samples can simply be taken. This is a crucial point for the principal. The material is then finely ground. of the Env. N. with a separate sample. Mn. Sonneveld. 176: 73-79.1 M hydrochloric acid or 1 % detergent solution. C. Fe. since this operation may change its chemical composition. Dry plant material can be stored for at least 10 years for the elements Al..A. Keizer. the milled plant material should pass a 1-mm sieve when less than 1 gram is to be weighed out. therefore. Mg. Wageningen. and P. 2. Besides.. Houba and Th. 13: 487-496. Na. it is necessary to collect as much plant material as possible in order to minimise variations due to heterogeneity. For comparability. physiological age and growth conditions. the plant material may attract moisture so that the drying procedure must be repeated just before weighing out a sample for analysis.G. Ca.J. REFERENCES 1. Plant Anal. Sampling and pretreatment 5 1. Influence of storage of plant samples on their chemical composition. Cl. Houba.M.Introduction. The analytical results are often referred to ‘oven-dry’ material. depending on its composition. The internal concentration of major nutrients will not significantly be affected by this treatment. dust and salts from irrigation water are the usual contaminants. Soil. Lexmond. P. S and Zn at laboratory conditions (Houba et al.. these stages are sufficiently important to mention here the main considerations and rules. Cu. however. V. Syllabus Department of Soil Science and Plant Nutrition. Cd. The drying at 105 oC should be done. 1995. Cu. dependent on plant part (leaf.3 SAMPLING AND PRETREATMENT Although the present manual is not intended to describe sampling and pre-treatment procedures for plant material.Soil Sci. . van der Lee. NO3-. Pb and possibly other heavy metals. Sampling of soil and plant material for chemical analysis. preceded by washing if the fresh plant material is (likely to be) polluted. During storage. K. stem.J. Fe. for instance. Novozamsky and J. I. M.G. V. 1982. the moisture content should be determined by drying at 105 oC and taking the difference with the 70 oC dried sample. 1984. The sample must be representative for the whole lot of plant material. As a rule of thumb. 3. van Dijk. Both drying and milling should be carried out with equipment that does not release elements for which the samples are to be analysed. The dried and milled samples should be stored in a cool and dry place in tightly closed flasks or in sealed polythene bags. protected against direct sunlight. if the washing does not take more than 30 s. One should realise. B. The Netherlands (in Dutch). The effectiveness of some washing procedures in the removal of contaminants from plant tissue samples of glasshouse crops. followed by rinsing with demi water. 1995). Pre-treatment of the sample involves drying and grinding. these may be washed out by tap water.

H2O2 AND SELENIUM 1. .3 Digestion tubes. 3. 2. DIGESTIONS 2. It can be applied for the determination of total calcium (Ca). 100 mL. manganese (Mn). sodium (Na).SALICYLIC ACID . phosphorus (P). 3. Salicylic acid is added to prevent loss of nitrate. PRINCIPLE 2.1 This digestion is in particular suited for routine work on large series of plant samples followed by automated determinations. and zinc (Zn) in plant material.1 The larger part of organic matter is oxidised by hydrogen peroxide at relatively low temperature. APPARATUS 3. with narrowed neck (Figure 2).2 Metal weighing funnels with long spouts (Figure 1). Figure 2 Digestion tube.1 DIGESTION IN TUBES WITH H2SO4 . nitrogen (N). the digestion is completed by concentrated sulphuric acid at elevated temperature under the influence of Se as a catalyst. FIELD OF APPLICATION 1. After decomposition of the excess H2O2 and evaporation of water. magnesium (Mg). Figure 1 Weighing funnel. potassium (K). 3.1 Aluminium heating block with holes for digestion tubes. 7 2.

3 g of the dried plant material sample in a metal weighing funnel and transfer the sample to a digestion tube. Dried plant material may easily stick to glass when the relative humidity of the air is low. Add 2.001-g. Digestion in tubes with H 2SO4 . Powder. Prepare also two blank digestions. . These known samples serve as internal quality control. Remarks: 5.3) in 1 litre of sulphuric acid (4.5 g of selenium (4. 2. Hydrogen peroxide must be of analytical quality.Dissolve 7.1 Sulphuric Acid.2 g of salicylic acid (4. 4. at that moment its moisture content is only 1-2 %. Powder.salicylic acid .5 mL of the digestion mixture (4. REAGENTS 3 4. Take care that all the plant material comes below the narrow part of the tube. or other interfering compounds. The entire process takes 3-4 hours. 4. 6.8 Digestions. the plant material is o dried again at 70 C just before weighing. 3.3 Selenium. Allow standing for at least 2 h. This digestion mixture should not be stored for more than 48 h. 96 % (w/w). These weighing funnels have been designed with an extra long spout.H2O2 and selenium Remarks: 1. have a narrowed neck and a length of at least 15 cm.2 Hydrogen Peroxide.6) and swirl carefully until all the plant material is moistened.5). to the nearest 0. a lower grade may be stabilised with EDTA. a series consists of 40 tubes: 34 samples. 1 plant sample with known low concentration (in duplicate) and 1 with known high concentration (also in duplicate).6 Digestion mixture . which results in loss of nitrate. 5. 4.4) in 100 mL of the sulphuric acid . 18 mol/L (U = 1.84 g/cm ).5 Sulphuric Acid . 4. In the authors' laboratory. as long as they fit exactly into the holes of the heating block used.4 Salicylic Acid. The originally black colour of the suspension turns via green/blue into clear light yellow. These homemade weighing funnels (stainless steel or aluminium) do not show this effect. the plant sample may contain up to 10 % moisture. 2 blanks. PROCEDURE 5. 4. where this digestion is applied every day.Dissolve 3. 30 % (w/w). In the authors' routine laboratory. When the drying is not repeated. 4. 4.1 Weigh.selenium mixture (4. In that case. while covering the beaker with a watch glass. so that concentrated sulphuric acid may be used for the digestion.2 (digestion in flasks).Selenium Mixture . The use of concentrated sulphuric acid then causes a raise in temperature. phosphate. diluted sulphuric acid should be used as described in section 2. approximately 0.1) by heating to about 300 oC. The dimensions of digestion tubes may be different from those indicated in Figure 2. so that the plant material is released below the narrowed neck.

6.5 mL for the blanks. Near the end of the digestion. it will dissolve in 18-20 hours after the addition of water.1 ± 0. 15. Soil Sci. Place the tube in the preheated heating block at 330 oC. Houba. it is appropriate to add a fixed volume of 48.Digestions. Add 48.1 mL for the samples. Remove the tube from the block. When Zn is to be determined. Commun. any volume marks on tubes lead to fairly large errors. and add successively three 1-mL aliquots of hydrogen peroxide (4.1 Novozamsky.6) lies just above 330 C. 16. 14: 239- 249. According to our experience. Allow to stand overnight. since the tubes are wide and the marks are often inaccurately placed. A novel digestion technique for multi-element plant analysis. o 8. WARNING: the reaction is violent.salicylic acid . The volume of digest is remarkably constant: 2. Thus.2). otherwise the digest has to be filtered soon after digestion. Therefore. The digestion is considered complete when the digests have turned colourless or light-yellow.J.H2O2 and selenium 9 Place the tube in the heating block and heat at 100 oC for at least 2 h. Digestion in tubes with H2SO4 . REFERENCES 6. this usually takes about 2 h. The boiling point of the digestion mixture (4. Mix carefully. R.2).8 M H2SO4. van Vark. o 9. the liquid becomes yellow due to the last portions of organic matter. After moistening the sample with digestion mixture (4. The final medium is 0. in the authors' laboratory this period is often taken overnight. then the presence of Fe should be assumed and the digestion can be considered as completed. A precipitate of CaSO4 may be formed when cooling after completing the digestion. no rubber stoppers should be used. Remarks: 7. For that reason. The filtered digest can be stored for a maximum of two weeks before analysis. 12. Place the tube again in the preheated block and heat at 330 oC. The calibration solutions for analysis have to be prepared in the same final medium as the samples in order to get a matrix. 1983. Wait until the reaction with hydrogen peroxide has ceased (approximately 10 s) before adding the next portion.. Mix again.G. cool and add another 1mL of hydrogen peroxide (4. 14. . 13. If the yellow colour persists after extra addition(s) of H2O2. transfer the digest to a test tube and let settle. I. Ca can be measured only after this period.3 mL of water and mix. which is the same as in the samples. when the block temperature o o is adjusted at 330 C. Remove the tube from the block and cool to room temperature. at least 2 h are needed for the nitro- salicylic acid compounds to be formed. van Eck and W. allow to cool. Plant Anal. 10. V. Wait for 1 h and if the colour of the digest is deep yellow. or to Fe. and 2. the determinations should be done soon after digestion. At least 2 h at 100 C is necessary to obtain complete reduction of the nitro-salicylic acid compounds. but thoroughly after each addition. 11. SiO2 will dissolve gradually and may then interfere in the determinations.3 mL water to the digest by means of a dispenser.6). the temperature in the tube will be approximately 300 C.

Digestion in flasks with H 2SO4 . The digestion is completed by hydrogen peroxide at elevated temperature. Remark: 1. . small series of plant samples. APPARATUS 3.1 This digestion is intended for incidental. 3.2 Metal weighing funnel (Figure 1).1 Hot plate. FIELD OF APPLICATION 1. Dried plant material may easily stick to glass when the relative humidity of the air is low. the plant material is dehydrated and most of the organic matter oxidised at rather high temperature.H2O2 2. Figure 1 Weighing funnel (measures in mm). nitrogen (N). able to reach 300 oC. PRINCIPLE 2. manganese (Mn). and zinc (Zn) in plant material. Salicylic acid is added to prevent loss of nitrate. magnesium (Mg).H2O2 1.2 DIGESTION IN FLASKS WITH H2SO4 .SALICYLIC ACID . It can be applied for the determination of total calcium (Ca). 2.1 With very strong sulphuric acid. 3. phosphorus (P).salicylic acid . Remark: 2. potassium (K). sodium (Na).10 Digestions. These homemade weighing funnels (stainless steel or aluminium) do not show this effect.

salicylic acid . and add 5 drops of hydrogen peroxide (4. The digest is filtered to remove any SiO2 that will otherwise dissolve gradually and then interfere in the determinations. Remove the flask from the plate. however. Allow to stand overnight. swirl until most of the precipitate has dissolved. If this reaches the neck of the flask. After moistening the sample with the digestion mixture (4.84 g/cm ).2). let cool down. Hydrogen peroxide must be of analytical quality. 18 mol/L (U = 1. 30 % (w/w). REAGENTS 3 4. Place the flask on the hot plate and increase the temperature to about 280 oC. add in small portions 100 mL of sulphuric acid (4. Add about 10 mL water and mix. PROCEDURE 5.3 mL of the digestion mixture (4. Make up to the mark with water. 4.5) and swirl carefully until all the plant material is moistened.4). o 6. 1 or 2 drops of hydrogen peroxide (4. 8.3 Salicylic Acid. A longer period (overnight). Heat 5-10 min until the water has evaporated (appearance of white vapours).4 Digestion Mixture . 4. Powder.1) (CAUTION). The addition of 10 mL water then produces enough heat to dissolve the precipitate rapidly. phosphate. Remarks: 5.H2O2 11 4. Since the dried sample still contains about 10 % (w/w) water.1. Remove the flask from the plate and cool to room temperature.4) and 4 carborundum beads (4. or other interfering compounds. 96 % (w/w). Take care that all the plant material comes below the neck of the flask.3) with the aid of a magnetic stirrer.2). let cool down.Put 18 mL water in a 250-mL erlenmeyer flask. Repeat this treatment until the digest has turned colourless. 7.2 Hydrogen Peroxide. to the nearest 0. .3 g of the dried plant material sample in a metal weighing funnel and transfer the sample to a 50-mL volumetric flask.001 g. While cooling.2) should be added. 4. approximately 0.1 Weigh. Digestion in flasks with H2SO4 .Digestions.1 Sulphuric Acid. mix well and filter over coarse filter paper. Remove the flask from the plate. 4. add 5 drops of hydrogen peroxide (4. and heat again for 5-10 min to appearance of white vapours. 4.5 Carborundum Beads Remarks: 3. will prevent foaming later on. Heat the flask on a hot plate at 180 oC for about 1 h. the sample will turn black and foam may be formed. at least 2 h is needed to form the nitro-salicylic acid compounds. remark 5). A precipitate may be formed when cooling after completing the digestion. Then dissolve 6 g of salicylic acid (4. Prepare also two blank digestions. Add 3. When heating at 180 C. 5. a lower grade may be stabilised with EDTA. the sulphuric acid is somewhat diluted to prevent the temperature from raising too high during addition of the digestion mixture which otherwise would result in loss of nitrate (see section 2.

it will dissolve in 18-20 hours after the addition of water. The calibration solutions for analysis have to be prepared in the same final medium as the samples in order to get a matrix.8 M H2SO4. Ca can be measured only after this period. which is the same as in the samples. 10. Therefore. then the presence of Fe should be assumed and the digestion can be considered as completed. A precipitate of CaSO4 may be formed when cooling after completing the digestion. Near the end of the digestion. 12. Do not use the volumetric flasks for other purposes. Digestion in flasks with H 2SO4 .salicylic acid . If the yellow colour persists after extra addition(s) of H2O2. 11. or to Fe. The final medium is 0. the liquid becomes yellow due to the last portions of organic matter.12 Digestions. .H2O2 9.

3. PRINCIPLE 2. manganese (Mn). ICP-OES. phosphorus (P). nickel (Ni). sodium (Na). copper (Cu).4 Microwave with lined digestion vessels (PTFE inner vessel with a polyetherimide outer vessel). tin (Sn).H2O2 . chromium (Cr). 3. Remark: 1. or ICP-MS) only. arsenic (As). with cylindrical holes in which the digestion vessels fit. The use of hydrofluoric acid. 3. 2. antimony (Sb).1 This digestion was developed for elemental analysis of plant tissue by means of spectrometric methods (Flame-AES. 3. potassium (K). In the author’s lab a CEM MDS 2100 microwave (1300 W output) is used.HF 13 2. AES.1 Metal weighing funnel (Figure 1). The fluoride is added in order to solubilise the plant tissue by destroying its silicate skeleton.2 Conventional hot plate. sulphur (S). . iron (Fe). cadmium (Cd).1 Hydrofluoric acid is allowed to react first and evaporate prior to the addition of hydrogen peroxide and nitric acid with subsequent microwave heating in a closed system.H2O2 . Treatment with HF is necessary to release any compounds absorbed to or included in the silicates. 3. nitric acid and hydrogen peroxide in one mixture followed by the microwave heating does not lead to complete dissolution in many cases. FIELD OF APPLICATION 1. The oxidation is incomplete. and therefore the digest can only be successfully analyzed by techniques such as AAS. magnesium (Mg). Complete dissolution is achieved with a high degree of mineralisation. Nitric acid oxidises most of the organic matter whereas hydrogen peroxide is needed to break down fatty components.HF 1.3 MICROWAVE DIGESTION WITH HNO3 . lead (Pb). calcium (Ca). vanadium (V) and zinc (Zn) in plant material. ICP-OES or ICP-MS. It can be applied for the determination of total aluminium (Al). cobalt (Co).Digestions. 50 mm thick. APPARATUS 3. ETA-AAS.3 Aluminium heating block. Flame-AAS. As a consequence Si and B cannot be determined. Microwave digestion with HNO3 . 2.

0 mL nitric acid (4. 30 % (w/w). Open the vessels in a fume hood.001 g. Close the vessels (hand tight) and place them in the digestor in the right sequence. approximately 0.4 mol/L (U = 1. 5. Check everything to be sure that the carrousel can turn free. Put the vessels into the holes of an aluminium block and let stand overnight at room temperature.2) and three times 1. Prepare also two blank digestions. 4. The homemade weighing funnels (stainless steel or aluminium) do not show this effect.H2O2 . See remark 6.40 g/cm ).4 g of the dried plant material sample in a metal weighing funnel and transfer the sample to the PTFE digestion vessel. PROCEDURE 5. 65 % (w/w). Add 4.1). Add 4.2) and mix well. REAGENTS 3 4. Remark: 4.2 Nitric Acid.1 Weigh. Evaporate to almost dry using a heating temperature of 120 °C.3-0. Dried plant material may easily stick to glass when the relative humidity of the air is low.Dilute 75 mL of concentrated aqueous ammonia (25 %) with water to 250 mL.0 mL of concentrated nitric acid (4.6 mol/L (U = 1.0 mL of the hydrofluoric acid (4.1 Hydrofluoric acid. Swirl carefully to moisten all the plant material and put the digestion inner vessel into the polyetherimide outer vessel. to the nearest 0. 22. 4.4 Ammonia Solution 4 mol/L .HF Figure 1 Weighing funnel (measures in mm). 40 % (w/w).3). Connect the pressure and temperature sensor tube to the pilot vessel.13 g/cm ). 4. Microwave digestion with HNO 3 . 3 4. 4. Switch on the microwave and start the digestion program (Table 1).14 Digestions. 14. Allow the vessels to cool down for 45 min after the program is finished or until the pressure is less than 60 psi. .3 Hydrogen Peroxide.0 mL of hydrogen peroxide (4.

Microwave digestion with HNO3 . van der Lee. Hydrofluoric acid is a treacherous skin poison. 8. the PTFE digestion vessel should be lifted from the block in order to prevent any charring. The evaporation of HF is slow in the beginning. As soon as the liquid has evaporated to dryness. If any HF comes into contact with the skin.1 Novozamsky. Commun.G.HF 15 Table 1 Operating parameters of the CEM microwave. REFERENCES 6.J. Then filter over fine paper into a polythene bottle.4) or calcium gluconate gel.H2O2 . this process should be observed frequently. Therefore. but very quick in the end.hydrogen peroxide in a closed system microwave digestor. Solubilization of plant tissue with nitric acid . The calibration solutions for analysis have to be prepared in the same final medium as the samples in order to get a matrix. 7. wash immediately and thoroughly with water and thereafter dab with 4 M ammonia (4. This is to be sure that the pressure in the other vessels is a slightly less.hydrofluoric acid . safety goggles and protective cloths. R.500 g. I. Houba and J. van Eck.J. The first vessel is the pilot vessel and should contain a standard plant sample of approximately 0. Stage 1 2 3 4 Power (%) 25 37 50 75 Maximum pressure (psi) 20 75 150 175 Run time (min) 1 5 5 10 Maximum temperature ( °C) 100 125 150 175 Fan speed (%) 50 50 50 50 Transfer quantitatively – with the help of a polythene funnel – to a 50-mL polythene volumetric flask. Remarks: 5. Plant Anal.4 M HNO3. 27: 867-875. 6. . Make up to the mark and mix. Since the first additions of HF and HNO3 are evaporated the final medium is 1. 6. 1996. which is the same as in the samples. Care should be taken that no solution drips out when the lid of the inner vessel is opened. Work in a good fume hood and wear rubber gloves. 9. V. Soil Sci..Digestions.

The fluoride is added in order to solubilise the plant tissue by destroying its silicate skeleton. arsenic (As). and therefore the digest can only be successfully analyzed by techniques such as AAS. The oxidation is incomplete.4 DIGESTION WITH HNO3 .2 Conventional hot plate. AES. or ICP-MS) only. PRINCIPLE 2. fitting the heating block holes (Figure 2). Remark: 1. nickel (Ni). sulphur (S).3 Aluminium heating block.HF 2.1 Boiling nitric acid oxidises most of the organic matter. cadmium (Cd). ICP-OES. 2. 3. cobalt (Co).H2O2 . magnesium (Mg). lead (Pb). vanadium (V) and zinc (Zn) in plant material. chromium (Cr).H2O2 . 3. 3. iron (Fe). Flame-AAS. calcium (Ca). antimony (Sb). APPARATUS 3.1 This digestion was developed for elemental analysis of plant tissue by means of spectrometric methods (Flame-AES. Hydrogen peroxide is needed to break down fatty components. phosphorus (P). Treatment with HF is necessary to release any compounds absorbed to or included in the silicates. ICP-OES or ICP-MS. tin (Sn). It can be applied for the determination of total aluminium (Al). FIELD OF APPLICATION 1. manganese (Mn). with cylindrical holes in which the digestion vessels fit.HF 1. . ETA-AAS. potassium (K).16 Digestions. 50 mm thick. As a consequence Si and B cannot be determined.1 Metal weighing funnel (Figure 1). 3.4 PTFE digestion vessels. copper (Cu). Digestion with HNO 3 . sodium (Na). homemade. 2.

Dilute 75 mL of concentrated aqueous ammonia (25 %) with water to 250 mL. Boil for 4 hours at 120 °C (see remark 4). See remark 7. to the nearest 0.4 mol/L (U = 1. (measures in mm). The part of the PTFE digestion vessel that sinks in the heating block has a thin wall for better heat transfer.001 g.HF 17 Figure 1 Weighing funnel Figure 2 Digestion vessel (measures in mm). Cover the digestion vessel with its lid and place the digestion vessel in a hole of the heating block. REAGENTS 3 4. Remove the lid and add 1 mL of hydrogen peroxide (4.0 mL of hydrogen fluoride (4. 65 % (w/w). 4. 40 % (w/w). 22.Add 138 mL of nitric acid (4.1 Nitric Acid.2 Hydrogen Peroxide.4 Nitric Acid Solution 2. Digestion with HNO3 .0 mol/L . Repeat the . Remarks: 2. 4. 14. whereas the upper part has a thick wall for better cooling. Allow the samples to stand overnight.2) to the still hot solution. Wait until the reaction has ceased (about 10 seconds) and keep on heating. PROCEDURE 5.3 Hydrogen Fluoride.5 Ammonia Solution 4 mol/L . 3 4.Digestions.13 g/cm ). the upper part must be high enough.1) to about 400 mL water and make up to 1 litre.6 mol/L (U = 1. approximately 2 g of the dried plant material sample in a metal weighing funnel and transfer the sample to the PTFE digestion vessel. For the same purpose. 4.H2O2 .3). Prepare also a blank digestion.1 Weigh. 4.1) and 5. The homemade weighing funnels (stainless steel or aluminium) do not show this effect. 3. Add 15 mL of concentrated nitric acid (4.40 g/cm ). 30 % (w/w). 5. Swirl carefully to moisten all the plant material. Dried plant material may easily stick to glass when the relative humidity of the air is low.

G. then transfer quantitatively – with the help of a polythene funnel – into a 100- mL polythene volumetric flask. If any HF comes into contact with the skin. A convenient method of digestion for elemental analysis of soil and plant material. Digestion with HNO 3 . The samples must be left with the acid mixture at room temperature for several hours (to prevent foaming later on). Plant Anal. the lid is essential to prevent premature evaporation of nitric acid. van der Lee. 8. Then filter over fine paper into a polythene bottle.4 M HNO3. Then add 10. 6. 1993.H2O2 .5 h before continuing the next morning with the rest of the procedure. Commun.HF addition of hydrogen peroxide twice. set the heating control at 140 °C and allow to evaporate until dry (CAREFUL see remark 5). Soil Sci. V. Hydrofluoric acid is a treacherous skin poison. Since the first additions of HF and HNO3 are evaporated the final medium is 0. the PTFE digestion vessel should be lifted from the block in order to prevent any charring.5) or calcium gluconate gel. . 5. remove the lid.J. Take up the residue in 20 mL of diluted nitric acid (4. Work in a good fume hood and wear rubber gloves. taking care that the solution does not start boiling. replace the lid and continue heating for 4 hours. the timer should be set at such a time that the heating starts just 4. wash immediately and thoroughly with water and thereafter dab with 4 M ammonia (4.0 mL of concentrated nitric acid (4.J. 24: 2595-2605.18 Digestions.4). safety goggles and protective cloths. I. but very quick in the end. and then be heated for 4 h at 120 °C. Therefore. As soon as the liquid has evaporated to dryness.. Make up to the mark.1 Novozamsky. The evaporation of HF is slow in the beginning. 7.5 h to reach the temperature of 110 ºC.1). The calibration solutions for determination have to be prepared in the same final medium solution as the samples in order to get a matrix. 6. this process should be observed frequently. and swirl. Since it takes about 0. REFERENCES 6. Houba and J. This can best be effected during the night by using a timer. In this procedure. Thereafter. Remarks: 4. Lower the temperature of the block and heat for 5-10 min. which is the same as in the samples. Allow cooling.

Other heating blocks and tubes may be used.4 PTFE tubes.5 DIGESTION WITH HNO3 1. (measures in mm). 3. with cylindrical holes in which the digestion vessels fit. provided that the tubes just fit the holes for efficient heat transfer. 3. homemade.Digestions. Digestion with HNO3 19 2. 2. but the extremely high temperature of the ICP causes all undigested compounds to atomise. FIELD OF APPLICATION 1. precisely fitting the heating block holes (Figure 2). 50 mm thick.2 Conventional hot plate. 3. Figure 2 Digestion tube.1 Boiling nitric acid oxidises most of the organic matter. APPARATUS 3. These homemade weighing funnels (stainless steel or aluminium) do not show this effect. Dried plant material may easily stick to glass when the relative humidity of the air is low.1 This digestion was especially developed for the ICP-OES determination of total sulphur (S). (measures in mm). 3. PRINCIPLE 2. Remark: 1. and rise high enough above the block for cooling. Figure 1 Weighing funnel.1 Metal weighing funnel (Figure 1). .3 Aluminium heating block. Remarks: 2. 3. This digestion is incomplete.

Prepare also a blank digestion.001 g. V.2). R. PROCEDURE 5.1 Weigh.J. Soil Sci. Cover the tube with its lid and allow to stand overnight.4 mol/L (U = 1. Remark: 4. 5.2 Nitric Acid Solution 4 mol/L . Temminghoff. van Eck. Remove the lid and allow the liquid to evaporate until about 1 mL remains.1) and swirl the tube carefully to moisten all the plant material. Determination of total sulphur and extractable sulphate in plant materials by inductively coupled plasma atomic emission spectrometry.2 M HNO3. 17: 1147-1157. Take up the residue in 5 mL of nitric acid (4. 4. The calibration solutions for analysis have to be prepared in the same digestion solution as the samples in order to get a matrix. Houba and E. I. let cool down. REFERENCES 6. Add 10 mL of concentrated nitric acid (4. Place the tube in a hole of the heating block and boil for 4 h at 120 oC. Plant Anal. J.1) to about 400 mL water and make up to 1 litre. 14.20 Digestions. to the nearest 0. 6. transfer to a 100-mL volumetric flask and make up to the mark.1 Novozamsky. boil for 10 min.Add 277 mL of nitric acid (4.1 Nitric Acid. Commun. approximately 1 g of the dried plant material sample in a metal weighing funnel and transfer the sample to the PTFE tube provided.J. 1986. REAGENTS 3 4. which is the same as in the samples. . van der Lee..G. 65 % (w/w). The final medium is 0.40 g/cm ). Filter over fine paper. Digestion with HNO3 4.

FIELD OF APPLICATION 1. Special safety precautions are necessary when using perchloric acid 3.H2SO4 21 2. 3. After the excess HNO3 is distilled off. 3. 1966) (Figure 2).6 DIGESTION WITH HNO3 .H2SO4 1.1 Heating mantles or blocks for 100-mL flasks. 1960). 3. APPARATUS 3.3 Digestion apparatus adapted from Chat (Chat. Remarks: 1. iron (Fe). 2.HCLO4 . which allows the determination of the trace elements. manganese (Mn). PRINCIPLE 2. copper (Cu).1 In this digestion a fairly large amount of plant material is weighed out.Digestions.HClO4 . 2. HClO4 oxidises the remaining organic compounds at elevated temperature. (measures in mm). This digestion method is also known as the "Schaumlöffel" method (Schaumlöffel. It can be applied for the determination of total cadmium (Cd).2 Metal weighing funnel (Figure 1). . Figure 1 Weighing funnel Figure 2 Digestion apparatus (measures in mm). Digestion with HNO3 . Sulphuric acid is present to "dilute" the perchloric acid in the final stage so as to prevent the risk of explosions.1 Easily oxidisable organic matter is attacked by HNO3 at relatively low temperature. and zinc (Zn).

96 % (w/w). During this process the contents of the flask turns black. approximately 2 g of the dried plant material sample in a metal weighing funnel and transfer the sample to the flat-bottomed 100-mL flask of the digestion apparatus. Digestion with HNO 3 . cool. or slightly coloured. The now concentrated perchloric acid attacks remaining organic material with a violent oxidation reaction.1) with 40 mL of perchloric acid (4. The stopcock should be closed.84 g/cm ).2) and add 10 mL of sulphuric acid (4. When the digest has turned colourless.4 Digestion Mixture . thereby collecting all liquid in the flat-bottomed digestion flask. the temperature will increase until the azeotropic boiling point of perchloric acid (205 oC) is reached. The Chat digestion apparatus as shown in Figure 2 is commercially available. Heat moderately (about 170 oC) for at least 40 min until most of the nitric acid has distilled off.Dissolve 0. Transfer the contents of this flask to a 100-mL volumetric flask. 3 4.4) and 4 carborundum beads (4. 4. without affecting the digestion process. Add 20 mL of the digestion mixture (4. Dried plant material may easily stick to glass when the relative humidity of the air is low. 4.6 Carborundum Beads. The dimensions of similar glassware from other suppliers may be slightly different. Prepare also two blank digestions. continue digestion for 1 h more. and rinse the side arm of the condenser. 18 mol/L (U = 1.2 Perchloric Acid. 14. Moisten the cone of the upper glass tube with water and place it on top of the condenser. 3 4. 5. 65 % (w/w). 70 % (w/w).40 g/cm ).6). 5. REAGENTS 3 4.5 Sodium Nitrite Solution 5 g/L .3 Sulphuric Acid. wash and collect these washings in the same .1 Nitric Acid. Then cool a little. Fix the whole digestion apparatus upright and allow to stand overnight at room temperature. Adjust the heat supply in such a way that these perchloric acid vapours condense halfway the side arm. When the distillation stops. These homemade weighing funnels (stainless steel or aluminium) do not show this effect. add about 20 mL water and 2 mL of sodium nitrite solution (4. 4.H2SO4 Remarks: 4.1 Weigh. so that a similar condenser (either purchased commercially or homemade) can be used as well.5).HClO4 .6 mol/L (U = 1. so that the remainder of nitric acid. in which dense white fumes are developed.3).Mix 400 mL of nitric acid (4. The stopcock is not necessary.67 g/cm ). PROCEDURE 5. discard the contents of the condenser.001 g. 11. Boil for 10 min. distils over.5 g of NaNO2 in 100 mL of water. to the nearest 0. together with some water. Then raise the temperature stepwise.22 Digestions. Wet the plant material by swirling the flask. 4.4 mol/L (U = 1. Moisten the lower cone of the condenser with water and place it on the flask.

E. 10. 1960. 12.2 Chat.HClO4 .H2SO4 23 volumetric flask and make up to the mark. Boiling is required to dissolve salts after the digestion. Académie d'Agriculture de France. 11. Since the additions of HClO4 and HNO3 are evaporated the final medium is 0. Zink. G. Remarks: 6. which might have been formed. Eisen und Molybdän aus einer Aschenlösung durch fraktionierte Extraktion. REFERENCES 6. Kobalt. The cones and stopcock must never be greased.1 Schaumlöffel.Digestions. 9. o 8. . which is the same as in the samples. Mix and filter over coarse paper into a 100- mL polythene bottle. The hot plates in the authors' laboratory are set at position 4-5 for 170 C and at 5. 6. Mangan. The calibration solutions for analysis have to be prepared in the same digestion solution as the samples in order to get a matrix. Sodium nitrite reduces insoluble higher oxides of manganese. Digestion with HNO3 . procès-verbal de la séance du 9 Novembre 1966: 1087-1093 (in French). 6.5 for 205 o C. 7. Nouvelle méthode de minéralisation des végétaux pour les analyses chimiques. Über die colorimetrische Bestimmung der Mikronährstoffe Kupfer. The plant material has to stand overnight with the digestion mixture to prevent excessive foaming.08 M H2SO4. 1966.5-6. This prevents any explosions due to too rapid reaction by perchloric acid. The first stage of the digestion should take at least 40 min to allow the nitric acid to destroy all the easily oxidisable material. but should be moistened with water. Landwirtschaftliche Forschung 13: 278-286 (in German).

It can be applied for the determination of total aluminium (Al). or ICP-MS) only.1 The organic matrix of the plant material is destroyed by controlled heating.2 Hydrochloric Acid. FIELD OF APPLICATION 1. antimony (Sb). 3. 36 % (w/w). Flame-AAS. PRINCIPLE 2. sodium (Na). 3. ICP-OES.7 DIGESTION BY DRY-ASHING FOLLOWED BY TREATMENT WITH HF 1. sulphur (S).13 g/cm ). 2. lead (Pb). manganese (Mn).2 Muffle furnace. See remark 5. 22.19 g/cm ). cadmium (Cd). 12. iron (Fe). Treatment with HF is necessary to release any compounds adsorbed to or included in silicates. As a consequence. 3.1 This digestion was developed for elemental analysis of plant tissue by means of spectrometric methods (Flame-AES. Digestion by dry-ashing followed by treatment with HF 2. nickel (Ni). Si and B cannot be determined. cobalt (Co). tin (Sn). REAGENTS 3 4.1 Hydrofluoric Acid. ETA-AAS. 4. Remarks: 1. . copper (Cu).24 Digestions. chromium (Cr). vanadium (V) and zinc (Zn) in plant material. 2. 40 % (w/w).1 Platinum or sintered aluminium oxide ("Alsint") crucibles. The required high temperature causes various nitrogen compounds to volatilise. APPARATUS 3. Silicates are removed as volatile fluorides. potassium (K). magnesium (Mg).4 Stirring rods. 3.0 mol/L (U = 1. arsenic (As).Dilute 75 mL of concentrated aqueous ammonia (25 %) with water to 250 mL.3 Ammonia Solution 4 mol/L . phosphorus (P).3 Hot plate. 3 4. calcium (Ca).6 mol/L (U = 1. 4.

Méthodes de référence pour la détermination des éléments minéraux dans les végétaux. Make up to the mark. add 2-3 mL of water and filter into the same volumetric flask. Book Temminghof-Proofs3 21-09-2004 Kolam Digestions. Heat the crucible on a hot plate until dry. Maintain this temperature during 0. heat until appearance of fumes.5 h. Raise the temperature gradually in 2 h to 450 oC. Then place the crucible in the cold muffle furnace and raise the temperature to 550 oC.2). Platinum crucibles should be cleaned as follows: Add to the crucibles a spoonful of potassium hydrogen sulphate. Add 5 mL of hydrofluoric acid (4. Remarks: 3. Rinse with water to remove the salt completely. Prepare also a blank digestion. Heat gently for some minutes on a hot plate (max. wash immediately and thoroughly with water and thereafter dab with 4 M ammonia (4. Cool. 5. Allow to cool.2). Work in a good fume hood and wear rubber gloves. Take the crucible out of the furnace and allow it to cool. Rotate the crucible while heating. Add 1 mL of hydrochloric acid (4. Place it in a muffle furnace at room temperature. 6. Note: Alsint crucibles should be cleaned with hot nitric acid. The calibration solutions for analysis have to be prepared in the same final medium as the samples in order to get a matrix. cool. Digestion by dry-ashing followed by treatment with HF 25 5. approximately 2 g of the dried plant material sample in a platinum or Alsint crucible.1 Membres du C. and maintain this temperature during 2 h. Put the filter paper and its contents into the same platinum or Alsint crucible and warm it gently in an oven until dry. Wait until the production of gas bubbles has stopped. Wash until acid-free. 80 oC) until the appearance of fumes.3) or calcium gluconate gel. taking care that the liquid does not boil (temperature about 100 oC). to the nearest 0. Add 2-3 mL of water and then carefully dropwise 1 mL of hydrochloric acid (4.12 M HCl. add 2-3 mL of water and filter over fine paper into a 100-mL volumetric flask. With Alsint crucibles the HCl procedure should be finished rapidly since the liquid "creeps" over the rim of the crucible. making use of a crucible tong with platinum tips.001 g.1 Weigh. PROCEDURE 5. .I.. Since the addition of HF is evaporated the final medium is 0. REFERENCES 6. Heat on top of a blue flame until the salt has dissolved.1). Allow to cool and dissolve the salt in warm water. Wash with lukewarm water till acid-free (< 50 mL total). 4. 1969. 6. which is the same as in the samples.I. safety goggles and protective cloths. Take the crucible out of the furnace and allow to cool. L'Agronomie Tropicale 24: 827-835 (in French). If any HF comes into contact with the skin. Hydrofluoric acid is a treacherous skin poison.

26 Digestions; Digestion by dry-ashing in the presence of CaO

2.8 DIGESTION BY DRY-ASHING IN THE PRESENCE OF CAO

1. FIELD OF APPLICATION

1.1 This digestion is intended for the spectrometric determination of B.

2. PRINCIPLE

2.1 The organic plant material matrix is destroyed by controlled heating. Boron
compounds are kept by calcium oxide.

3. APPARATUS

3.1 Porcelain crucibles.

3.2 Hot plate.

3.3 Muffle furnace.

3.4 Polythene stirring rods.

4. REAGENTS

4.1 Calcium Oxide Finely Powdered.

4.2 Sulphuric Acid Solution 0.5 mol/L - Add carefully, while swirling, 28 mL of
concentrated sulphuric acid (96 %) to about 400 mL water in a 1-L volumetric flask.
Let cool down and dilute to volume.

5. PROCEDURE

5.1 Weigh, to the nearest 0.001 g, approximately 1 g of the dried plant material sample in
a porcelain crucible. Add 100 mg of calcium oxide (4.1) and mix thoroughly until no
CaO particles can be distinguished any more from the plant material. Prepare also a
blank digestion.
Place the crucible on a preheated hot plate (about 200 oC) and heat until the sample
has charred completely. Take care that the sample does not start burning. Cool the
charred sample and place it in a muffle furnace. Raise the temperature to 500 oC and
maintain this temperature for 1.5 h. Take the crucible out of the furnace and allow to
cool.
Add 10 mL of sulphuric acid (4.2). Let stand for 30 min and stir several times during
this period. Filter over coarse paper into a polythene tube.

Digestions; Digestion by dry-ashing in the presence of CaO 27

Remarks:
1. With the precipitate of CaSO4 that has been formed after the addition of sulphuric acid other
compounds will coprecipitate so that interferences are diminished.
2. The calibration solutions for analysis have to be prepared in the same digestion solution as the
samples in order to get a matrix, which is the same as in the samples. Since part of the sulphuric
acid is consumed by the calcium oxide, the final medium is approximately 0.35 M H2SO4.

6. REFERENCES

6.1 Gupta, U.C. 1967. The boron determination of some plant materials as determined
with and without adding CaO before ashing. Plant Soil 26: 202-204.

28

3. EXTRACTIONS

3.1 EXTRACTION WITH WATER
1. FIELD OF APPLICATION

1.1 This extraction is meant for the determination of chloride (Cl-), nitrite-nitrogen (NO2-),
nitrate-nitrogen (NO3-) and sulphate-sulphur (SO42-).

2. PRINCIPLE

2.1 The anions that are "free" in the plant material are extracted as such by water.

3. APPARATUS

3.1 Metal weighing funnel (Figure 1).

3.2 Shaker, linear or end-over-end.

3.3 Filter Paper, Fine, Cl free.

Remark:
1. Dried plant material may easily stick to glass when the relative humidity of the air is low. These
homemade weighing funnels (stainless steel or aluminium) do not show this effect.

Figure 1 Weighing funnel (measures in mm).

4. PROCEDURE

4.1 Weigh, to the nearest 0.001 g, approximately 0.5 g of the dried plant material sample
in a metal weighing funnel and transfer the sample to a 50-mL erlenmeyer flask. Add
25 mL water and shake for 30 min at room temperature. Filter over fine paper (4.1).

The final medium is water. since the filtrates will rapidly turn turbid due to mould growth. . Use the last filtrate for analysis. The determinations must be carried out on the same day as the extraction. The calibration solutions for analysis have to be prepared in the same final medium as the samples in order to get a matrix. The first filtration will clog the paper just enough to obtain a more clear filtrate at the second time. Extraction with water 29 Collect the filtrate and filter this very portion of filtrate again over the same piece of paper. 3. which is the same as in the samples.Extractions. 4. Remarks: 2.

Only polythene flasks etc.13 g/cm ). Extraction with HF . See remark 5.HCl 3. 3.1 This extraction is only appropriate for the determination of boron (B) and silicon (Si). respectively. 3.Mix 100 mL of hydrofluoric acid (4. The extracts are coloured brown.4 Polythene volumetric flasks.2 EXTRACTION WITH HF . REAGENTS 3 4. 3. FIELD OF APPLICATION 1.HCL 1.5 Polythene graduated cylinders.6 mol/L (U = 1. 3. If a sample contains both Si and K in large concentrations.Dilute 75 mL of concentrated aqueous ammonia (25 %) with water to 250 mL. 12. APPARATUS 3.0 mol/L (U = 1. 3.2 Hydrochloric Acid.30 Extractions. so that spectrometric determinations are not possible. . 40 % (w/w). 3.4 Ammonia Solution 4 mol/L . 4.1) with 40 mL of hydrochloric acid (4. 3.3 Polythene funnels.1 Borates and silicates are extracted from the plant material as tetrafluoroborates and hexafluorosilicates.3 Extraction Mixture . 2. the slightly soluble K2SiF6 may be formed. can be used because glass contains Si. 4.1 End-over-end shaker.5 M in HF and 1 M in HCl.1 Hydrofluoric Acid. 3 4. PRINCIPLE 2. Remarks: 1. 36 % (w/w).19 g/cm ). A larger extraction ratio should then be used.2) and add 360 mL water.6 Pipettors with polythene tips. This extraction solution is 4. 2. 22.2 Polycarbonate test tubes and caps. 4.

18: 789- 802. J.. safety goggles and protective cloths. Manyeki. V. Commun.J. Determination of boron in fresh and in dried plant material by plasma emission spectrometry after extraction with HF-HCl. Novozamsky. I. 6. 6. Soil Sci. Plant Anal. Prepare also a blank extraction. Hydrofluoric acid is a treacherous skin poison. 5.1 Weigh.001 g. If Si has to be measured. Laboratory coats fresh from the laundry might release boron (from the perborate used in washing powder). Add 10 mL of extraction mixture (4. van Eck and V.Soil Sci.3) and moisten the plant material by shaking manually. which is the same as in the samples. to the nearest 0. Commun. A rapid determination of silicon in plant material. Remarks: 4.HCl 31 5. Walinga. The calibration solutions for analysis have to be prepared in the same final medium as the samples in order to get a matrix.G. Houba. The final medium is 1.K. P. Since normal demineralised water may contain varying concentrations of Si. wash immediately and thoroughly with water and thereafter dab with 4 M ammonia (4. PROCEDURE 5. I. 6. R. Shake overnight at room temperature. Work in a good fume hood and wear rubber gloves. the use of ultra pure water is strongly advised. Filter the suspension over medium fine paper.J.J. REFERENCES 6. 0.3 g of the dried plant material sample into a polycarbonate test tube. Houba and I.1 Novozamsky.Plant Anal.0 M HCl and 4.G.5 M HF.. approximately 0.15 g K2SiF6 can be added as a check (see remark 1).Extractions.2 Van der Lee. 15: 205-211. 7. 1984.4) or calcium gluconate gel. . 1987. Extraction with HF . If any HF comes into contact with the skin.

2. REAGENTS 6.1 Aluminium ions form – in weakly acid medium and in the presence of a polycyclic ketoamine – an extremely stable. APPARATUS 5. 3. 5.1 The procedure yields a standard curve that is linear up to approximately 5 mg/L Al.3 (microwave digestion with HNO3 . a coefficient of variation within 8 %. the only possible interference comes from Fe(III).1 The polycyclic ketamine reagent is specific for Al. RANGE AND DETECTION LIMIT 2.HF).1 Spectrophotometer.2 This determination may be carried out on digest 2.H2O2 . 6.4 (digestion with HNO3 .7 (digestion by dry-ashing followed by treatment with HF). digest 2. at reasonable control and thorough sample preparation.1 DETERMINATION OF ALUMINIUM 4. . 1. PRINCIPLE OF METHOD 1.19770. Any Fe interference is prevented by addition of ascorbic acid.1 The reproducibility of determinations by this procedure should give. The determination limit is approximately 60 Pg/L (3.Merck nr 1. 4. Al concentration 1000 mg/L . INTERFERENCES 3.1A Stock Solution.2 The detection limit is approximately 20 Pg/L in the digest.1. The intensity of the red-coloured complex can be measured with a spectrophotometer at a wavelength of 595 nm.H2O2 .0 mg/kg in the dried plant material).HF) and digest 2. red-coloured complex with Eriochrome Cyanine R.A DETERMINATION OF ALUMINIUM BY SPECTROPHOTOMETRY 1.32 4. PRECISION AND ACCURACY 4. but only at concentrations which are normally not found in plant material. 2. DETERMINATIONS 4.

12 Mixed Reagent .A heterocyclic fatty acid amine.Determinations. 6.56 mol/L .20 mol/L . Prepare fresh daily. Alphen a/d Rijn. (or 2. Add 50 mL of ammonium nitrate solution (6. Add 225 mL water and mix. Al concentration 50 mg/L . 6.12H2O may lose crystal water on standing. KAl(SO4)2.0 mL stock solution (6.4 Ammonium Nitrate Solution 1.Mix 50 mL of sulphite solution (6. or from N. C6H8O6. in 50 mL water. Add 2 mL of concentrated nitric acid (65 %) and mix.11 Acetate Solution 2.9 Sulphite Solution 0. 6.2 Standard Solution. Determination of aluminium 33 6. . 6.7 Diluted Eriochrome Cyanine R Solution . Prepare fresh daily.25 g of sodium chloride.5 Sodium Chloride Solution 2. The reagent should be standardised by adding an excess of EDTA with ZnSO4 and back-titration with Eriochrome Black T as an indicator. Pa. KAl(SO4).12H2O.1A or 6. Make up to 1000 mL with water.3H2O. 6.5 g of sodium sulphite heptahydrate) in 50 mL water.11). Inc. 6.Dissolve 1 g of ascorbic acid. in 50 mL water. Ambler. 6. to be purchased from Amchem Products. 6.7 g of polycyclic ketoamine (6. Mavom.25 g of ammonium nitrate..94 mol/L . Na2SO3.9) with 50 mL of polycyclic ketoamine solution (6.6).4) and mix. NH4NO3. NaCl. Al concentration 1000 mg/L . Make up to 250 mL with water. Prepare fresh daily.25 g of sodium sulphite.3 Polycyclic Ketoamine .43820) in 50 mL water.V. in water and make up to 50 mL.1B) in a polythene 1000-mL volumetric flask and make up to volume with water. The Netherlands.6 Eriochrome Cyanine R Solution .14 mol/L . 6.Dissolve 6.3) in 100 mL water.Dissolve 6.5) and mix.10) and 50 mL of acetate solution (6.Dissolve 1. Add 50 mL of sodium chloride solution (6. in 50 mL water.8 Ascorbic Acid Solution . Handelsweg 6.Dissolve 17. nr. 6.Pipette 50. USA.1B Stock Solution. CH3COONa . Remark: 1.Dissolve 0.Dissolve 250 mg of Eriochrome Cyanine R (C.I.10 Polycyclic Ketoamine Solution . Prepare fresh daily. in a volumetric flask of 1000 mL.Add 60 mL water to 40 mL of the Eriochrome Cyanine R solution (6. Do not use rubber stoppers.Dissolve 20 g of sodium acetate trihydrate. 6.5760 g potassium aluminium sulphate dodecahydrate.

0 mL mixed reagent (6. mix and wait for 5 min x 3. in mg/L. CALIBRATION AND STANDARDS 7. in mg/L. w is the weight of plant material sample. PROCEDURE 8. The pH of the final solution should lie between 5. 1966. The absorbance will increase with pH by 0.Pipette 0.0 mL concentrated nitric acid (65 %) (digestion 2.8). Make up to the mark with water.20 mL of the standard series. b is the concentration of aluminium in the blank digest. is calculated by: (a . Chem.1 Hill. This standard series has Al concentrations of 0 – 1 – 2 – 3 – 4 – 5 mg/L. CALCULATION 9. U.00 – 10.b) * V / w in which: a is the concentration of aluminium in the sample digest.0 mL diluted Eriochrome Cyanine R solution (6.656.4) or 1. Add successively: x 1. to prevent Al desorption and to cleanse it from polycyclic ketoamine.00 mL of the standard solution (6. 9.Pipette 0 – 2. expressed in mg/kg Al.0 mL ascorbic acid solution (6. mix and wait for 1 h Measure the absorbance in a 1-cm cuvette at a wavelength of 595 nm. in mL. since this is contaminated by aluminium. Remarks: 1. 38: 654 .2 Calibration Curve .0 mL concentrated hydrochloric acid (65 %) (digestion 2. 10. All glassware must be pretreated with "chromic acid".1 The aluminium content of the dried plant material.3).02 units per pH unit. the blanks and the sample digests into test tubes.7). 3. Anal.7). spelter. V is the total volume of digest at the end of the digestion procedure. Do not use a detergent.00 – 4.5 and 5. 7.The absorbance (A) is plot versus mg/L aluminium in the standard series. Determination of aluminium 7. The colour of the measuring solution is stable for 2 h. 8. mix and wait for 5 min x 1.2) into 100-mL volumetric flasks which already contain 40 mL water and add either 10 mL concentrated nitric acid (65 %) (digestion 2. in g.1 Measurement . 3.1. New direct spectrophotometric determination of aluminium in steel. REFERENCES 10.1 Standard Series .00 – 8. and iron ores.00 – 6. Transfer the solutions to polythene bottles. 2.12).T. .34 Determinations.

Make up to 1000 mL with water. KAl(SO4)2. .H2O2 .10 mg/L (12 respectively 33 mg/kg Al in the dried plant material).1. Aluminium compounds are dissociated and excited. 4. digest 2.1 The reproducibility of determinations by this procedure should give. REAGENTS 6. in a volumetric flask of 1000 mL.1 Solutions with aluminium compounds are nebulised into an argon plasma.1 Inductively coupled plasma optical emission spectrometer. and then emit radiation of which the intensity is measured at a wavelength of 237. Al concentration 1000 mg/L . 6. 2.1 This procedure yields a standard curve that is linear up to at least 100 mg/L Al. a coefficient of variation within 5 % + 5 mg/kg.4 (digestion with HNO3 .7 (digestion by dry-ashing followed by treatment with HF).12H2O. 2. where all components are vaporised. Determination of aluminium 35 4. 5.19770. 3. PRECISION AND ACCURACY 4. PRINCIPLE OF THE METHOD 1.2 This determination may be carried out on digest 2.B DETERMINATION OF ALUMINIUM BY ICP-OES 1.2 The detection limit is approximately 0. Al concentration 1000 mg/L .3 (microwave digestion with HNO3 .Merck nr 1. RANGE AND DETECTION LIMIT 2.1B Stock Solution. APPARATUS 5.1A Stock Solution.H2O2 .Dissolve 17. INTERFERENCES 3.HF) and digest 2.1 No interferences are expected.HF). at reasonable control and thorough sample preparation.Determinations. 1.035 mg/L in the digest. 6. The determination limit is approximately 0.5760 g potassium aluminium sulphate dodecahydrate.312 nm.

Co. is calculated by: (a .1 Measurement . in mg/L. S and Zn). V is the total volume of digest at the end of the digestion procedure. expressed in mg/kg Al. Let cool down and make up to the mark with water. 7. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series.235 nm. A data management system and system controller are used. Mn. in mL.00 mL of the standard solution (6.00 – 2.1 The total aluminium content in the dried plant material. b is the concentration of aluminium in the blank digest. .Measure in the standard series. At this wavelength a (fitted) background correction is used. Remarks: 3.Pipette 0 – 1. Cr Cu.1 Standard Series .1) into 100-mL volumetric flasks which already contain 40 mL water and add either 10 mL concentrated nitric acid (65 %) (digestion 2.12H2O may lose crystal water on standing.The emission counts are plot versus mg/L aluminium in the standard series. Cd. 7. at a wavelength of 255. PROCEDURE 8. K. in g.0 mL concentrated nitric acid (65 %) (digestion 2.3). in mg/L. CALCULATION 9. Scandium (5 mg/L).7). Na. the blanks and the sample digests the Al concentration with the ICP-OES at a wavelength of 237.b) * V / w in which: a is the concentration of aluminium in the sample digest.0 mL concentrated hydrochloric acid (65 %) (digestion 2.312 nm. This standard series has Al concentrations of 0 – 10 – 20 – 100 mg/L.2 Calibration Curve . 9.4) or 1. 3. Mg. Ni P. KAl(SO4)2. Determination of aluminium Remark: 1.36 Determinations. Ca. Fe. w is the weight of plant material sample.00 – 10. The reagent should be standardised by adding an excess of EDTA and back-titration of the excess EDTA with ZnSO4 solution with Eriochrome Black T as an indicator. In this way the measurements are checked continuously and the data output is in concentration units in the digests. As a check all standards can be measured as samples. 8. A mix standard series can be used for simultaneous measurements with ICP-OES (Al. 4. is used in the author's laboratory as an internal standard to compensate for matrix effects. Remark: 2. CALIBRATION AND STANDARDS 7. 5.

Make up to 1000 mL with ultra pure water. The determination limit is approximately 1. PRECISION AND ACCURACY 4. APPARATUS 5.) in a 100-mL polythene volumetric flask which already contains about 50 .1.7 (digestion by dry-ashing followed by treatment with HF). REAGENTS 6.p. 2.1 This procedure yields a standard curve that is linear up to at least 1000 Pg/L Al.12H2O.1 Interferences are expected from 54Fe++ and 11B16O due to mass overlap with 27Al.Determinations.3 respectively 4 mg/kg in the dried plant material). 6.4 µg/L in the digest. 6. Al concentration 1000 mg/L . Determination of aluminium 37 4.2 µg/L (1. in a volumetric flask of 1000 mL. and quantified with a channel electron multiplier.1A Stock Solution.Merck nr 1.2 The detection limit is approximately 0. 6. Aluminium is determined at mass 27 amu.4 (digestion with HNO3 . 2. 4.5760 g potassium aluminium sulphate dodecahydrate.2 This determination may be carried out on digest 2. sorted according to their mass-to-charge ratios. PRINCIPLE OF THE METHOD 1.HF) and digest 2. digest 2. 1. at reasonable control and thorough sample preparation.1 The reproducibility of determinations by this procedure should give.19770. Al concentration 1000 mg/L . INTERFERENCES 3. a coefficient of variation within 10 %.2 Standard Solution.HF). The ions produced are entrained in the plasma gas and introduced into a mass spectrometer. where all components are vaporised. KAl(SO4)2.Pipette 1 mL concentrated nitric acid (65 % s.Dissolve 17.H2O2 . Al concentration 20 mg/L .1B Stock Solution. 3.3 (microwave digestion HNO3 - H2O2 .1 Inductively coupled plasma mass spectrometer.1 Solutions with aluminium compounds are nebulised into an argon plasma. 5. RANGE AND DETECTION LIMIT 2.C DETERMINATION OF ALUMINIUM BY ICP-MS 1.

0 mL concentrated nitric acid (65 %) (digestion 2. Ni. PROCEDURE 8.38 Determinations. Make use of corrections if necessary. 0. Sb.3 mL concentrated nitric acid (65 %) (digestion 2. Pb. The reagent should be standardised by adding an excess of EDTA with ZnSO4 and back-titration with Eriochrome Black T as an indicator. the blanks and the sample digests the Al concentration with the ICP-MS at a mass of 27 amu.1 Standard Series . 7. in Pg/L. Cu.12H2O may lose crystal water on standing. w is the weight of plant material sample. expressed in mg/kg Al. As. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series.00 mL of the standard solution (6.3).1A or 6. in mL. KAl(SO4).b) * V / w in which: a is the concentration of aluminium in the diluted sample digest. 7. Remark: 2. As a check all standards can be measured as samples. CALIBRATION AND STANDARDS 7. Mn.01 * (a . V is the total volume of digest at the end of the digestion procedure. Determination of aluminium mL ultra pure water. 9. Measure in the standard series. A data management system and system controller are used.pipette 0 – 1. b is the concentration of aluminium in the diluted blank digest. 8.7). Sn. is calculated by: 0. Cr. Co.00 – 5. Remark: 1. Cd. V and Zn).The counts per second are plot versus Pg/L aluminium in the standard series.4) or 0.1 The total aluminium content in the dried plant material. This standard series has Al concentrations of 0 – 200 – 400 – 1000 µg/L. . 4. Add 2.00 mL stock solution (6.2) in a 100-mL polythene volumetric flasks which already contain 40 mL ultra pure water. A mix standard series can be used for simultaneous measurements with ICP-MS (Al. in g. In this way the measurements are checked continuously and the data output is in concentration units in the digests. CALCULATION 9.1 Measurement – Dilute the blanks and the sample digests 1 + 9 (v/v) with ultra pure water and mix.2 Calibration Curve . Remarks: 3. in Pg/L.1B) and make up to volume with ultra pure water. Add either 1. Let cool down and make up to the mark with ultra pure water.00 – 2.1 mL concentrated hydrochloric acid (36 %) (digestion 2.

RANGE AND DETECTION LIMIT 2. PRINCIPLE OF THE METHOD 1.2 The detection limit is approximately 0.1 Stock Solution. A correction factor for ArCl can be used. INTERFERENCES 3.1 Solutions with arsenic compounds are nebulised into an argon plasma. 2.1 Inductively coupled plasma mass spectrometer. The determination limit is approximately 0.4 (digestion with HNO3 . APPARATUS 5.3 (microwave digestion with HNO3 . 63Cu12C due to mass overlap at 75 As. 1.Pipette 1 mL concentrated nitric acid (65 % s.2 This determination may be carried out on digest 2. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer. sorted according to their mass-to-charge ratios. PRECISION AND ACCURACY 4.A DETERMINATION OF ARSENIC BY ICP-MS 1. 40Ca35Cl. The correction affects also the detection limit. at reasonable control and thorough sample preparation.Determinations.H2O2 .Merck nr 1.2. 6. where all components are vaporised. Arsenic is determined at mass 75 amu. 6. 2. a coefficient of variation within 10 %. 5.007 µg/L in the digest. and quantified with a channel electron multiplier. Determination of arsenic 39 4.) in a 1000-mL polythene volumetric flask which already contains about .HF) and digest 2. As concentration 1 mg/L .1 This procedure yields a standard curve that is linear up to at least 50 Pg/L As.p.HF).7 (digestion by dry-ashing followed by treatment with HF).2 DETERMINATION OF ARSENIC 4. 4.02602.021 µg/L (2 respectively 7 µg/kg in the dried plant material).2 Standard Solution.1 Interferences are expected from 40Ar35Cl. digest 2.H2O2 .1 The reproducibility of determinations by this procedure should give. 3. As concentration 1000 mg/L . REAGENTS 6.

1 Measurement . in g. Cr.2 Calibration Curve . Remarks: 2. As. b is the concentration of arsenic in the blank digest. 8. Sn.3). Add either 1. A mix standard series can be used for simultaneous measurements with ICP-MS (Al. V and Zn). Cu. Let cool down and make up to the mark with ultra pure water.00 mL stock solution (6. Co.40 Determinations. Make use of corrections if necessary.3 mL concentrated nitric acid (65 %) (digestion 2. 0.2) in a 100-mL polythene volumetric flasks which already contain 40 mL ultra pure water. 3. CALCULATION 9.1 The total arsenic content in the dried plant material. . V is the total volume of digest at the end of the digestion procedure. In this way the measurements are checked continuously and the data output is in concentration units in the digests.Measure in the standard series. expressed in µg/kg As.pipette 0 – 1. in Pg/L.00 – 5. the blanks and sample digests the As concentration with the ICP-MS at a mass of 75 amu.1) and make up to volume with ultra pure water. Determination of arsenic 500 mL ultra pure water. Cd.00 – 2.b) * V / w in which: a is the concentration of arsenic in the sample digest. w is the weight of plant material sample. Sb. is calculated by: (a . in Pg/L. PROCEDURE 8.The counts per second are plot versus Pg/L arsenic in the standard series.1 mL concentrated hydrochloric acid (36 %) (digestion 2. CALIBRATION AND STANDARDS 7.4) or 0. A data management system and system controller are used. Mn. Ni. 7. Add 1. 7.00 mL of the standard solution (6.7). in mL.0 mL concentrated nitric acid (65 %) (digestion 2. Remark: 1. This standard series has As concentrations of 0 – 10 – 20 – 50 µg/L. As a check all standards can be measured as samples. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series.1 Standard Series . 9. Pb.

19500. APPARATUS 5.1 Polythene test tubes with covers (because of bad smell).1 Al.1 The reproducibility of determinations by this procedure should give.2 The detection limit is approximately 0. 6. RANGE AND DETECTION LIMIT 2. 3.3 mg/L (3 mg/kg dried plant material). 2.Determinations. INTEFERENCES 3.1 Borate ions form a red coloured compound with Azomethine-H at pH 4-5. Determination of boron 41 4. 2.3. PRECISION AND ACCURACY 4. at reasonable control and thorough sample preparation.3 DETERMINATION OF BORON 4. The absorbance of the complex is measured at a wavelength of 430 nm. 5. PRINCIPLE OF METHOD 1. 5.1A Stock Solution. Thioglycollic acid is used to mask Fe.2 Spectrophotometer with interference filter. 2. . Remarks: 1.8 (digestion by dry-ashing in the presence of CaO). Interference from Al and Cu is prevented by addition of EDTA. 1. 4. REAGENTS 6.1 This procedure yields a standard curve that is linear up to approximately 2 mg/L B.2 This determination may be carried out on digest 2.1 mg/L in the digest. Cu and Fe may interfere. a coefficient of variation within 10 %. The determination limit is approximately 0.Merck nr 1.A DETERMINATION OF BORON BY SPECTROPHOTOMETRY 1. B Concentration 1000 mg/L .

causes loss of water and conversion to metaboric acid.Dilute 5.10H2O. 6.5719 g H3BO3 per litre.50 – 1.819 g of borax (sodium tetraborate decahydrate). B concentration 50 mg/L . Add 2. Prepare fresh daily.1A or 6. in 160 mL water. Store in polythene bottles. or even storage in a desiccator. This o compound should be used as such.00 mL of the standard solution (6.0 mg/L. 7.25 – 0.2H2O in the mixture. 15 mL ethanol and finally with 15 mL of diethyl ether.6 Mixed Buffer Solution. the use of boric acid.9 g of Azomethine-H (6.3). Borax easily loses crystal water on standing. For the same reason.0 mL concentrated sulphuric acid (96 %) (digestion 2. 3 6.5 Azomethine-H Mixture . (see remark 3) in some water in a 1000- mL volumetric flask and make up to volume.Pipette 0 – 0.4 Azomethine-H (4-Hydroxy-5[Salicylidene-Amino]-2. First dissolve 30 g borax 100 mL water. U = 1. Na2B4O7. Dissolve 2.1B) with water to 100 mL. 1978). this must be filled with 4 M HNO3 and left overnight before cleaning in the usual manner. Determination of boron 6. 4. then filter the newly formed crystals on a Büchner funnel by suction. . After the final washing.2) into 100-mL volumetric flasks which already contain 40 mL water and add 2. To be sure that the salt contains 10 molecules of crystal water it has to be recrystallised. Store in a polythene bottle.1 Standard series . since the colour to be measured fades when using the freshly prepared buffer. To avoid any problems with borax. 6.0 – 1. The mixed buffer solution (6. 6. H3BO3.00 – 2.Dissolve 8.00 – 3.42 Determinations. mix well and allow to stand overnight. Wash twice with 15 mL water. the solid has to be dried on a watch glass at room temperature for 12-18 h (Besset.2 Standard Solution. It is assumed that the thioglycollic acid (6. B Concentration 1000 mg/L . Store in a polythene bottle.6) should be used only after standing overnight.9 .7-Naphtalene Disulphonic Acid. CH3COONH4.00 – 4.3) is responsible for this effect. C17H13NO8S2). C2H4O2S.68 g of Na2EDTA.1B Stock Solution.00 mL of the stock solution (6. pH 4. A stock solution of 100 mg/L B will contain 0. Remarks: 3.Dissolve 2 g of ascorbic acid and 0. HBO2.32 g/cm ). may be considered.8). 5. 6.3 Thioglycollic Acid. Each washing must be followed by suction to remove the liquid.4) in some water and make up to 100 mL in a polythene flask.50 – 1. CALIBRATION AND STANDARDS 7. Prepare fresh weekly. because drying at 105 C. This standard series has B concentrations of 0 – 0. Let cool down and make up to volume with water.Dissolve 100 g of ammonium acetate.4 mL of thioglycollic acid (6. Store in a polythene bottle. To prevent desorption of borate from the glassware to be used.5 – 2. 6. reagents and standard solutions should be transferred to polythene vessels directly after preparation. 98 % (Mercaptoacetic Acid. et al. Add 50 mL of concentrated acetic acid (100 %) and mix.

9. Longman. p.4 Besset. The calibration curve should be linear. Commun. in mL. 9. is calculated by: (a . den Dekker and P.A.3 Wolf. B. w is the weight of plant material sample. 8. The zero standard normally reads 0.1 Wolf. PROCEDURE 8.0. in mg/L. van Dijk. 10.225 Abs and the highest standard usually reads 0. Internal communication of the Glasshouse Crops Research Station. 10. B. London. water and nutrient solutions. 1974. the blanks and the sample digests into polythene test tubes. CALCULATION 9. 8. in mg/L. Measure the absorbance in a 1-cm cuvette at a wavelength of 430 nm after 30 min and within 1. Improvement of the Azomethine-H method for the determination of boron. Soil Sci. Soil Sci.0 mL of mixed buffer solution (6. .1 The boron content of the dried plant material. V is the total volume of digest at the end of the digestion procedure. The Netherlands (in Dutch). P.590 Abs. Plant Anal.6) and mix thoroughly. Instead of the 410 nm mentioned in literature. manures. 1971.190 . S. 1978. Commun.A. 10. 430 nm was chosen for absorbance measurement because the background absorption of the reagent is much lower at this wavelength. Vogel's textbook of quantitative inorganic analysis. 4th edition. The determination of boron with Azomethine-H in plant material.1 Pipette 2.2 Calibration Curve . expressed in mg/kg B.0. REFERENCES 10. Determination of boron 43 7. 10. The determination of boron in plant material extracts. Add 4. plant materials. soil and water.The absorbance (A) is plot versus mg/L boron in the standard series.2 De Bes. composts. Remarks: 7.Determinations.b) * V / w in which: a is the concentration of boron in the sample digest. 300.S. 5: 39-44. b is the concentration of boron in the blank digest. Laboratory coats fresh from the laundry might release boron (from the perborate used in washing powder).550 .0 mL of Azomethine-H mixture (6.00 mL of the standard series. J et al. in g. 2: 363-374.5 h.5) and mix again thoroughly. 1973. Add 2. Naaldwijk. Plant Anal.

PRECISION AND ACCURACY 4. .002 mg/L in the extract. The determination limit is approximately 0.3.1 The reproducibility of determinations by this procedure should give. 5.2 This determination may be carried out on extract 3.006 mg/L (0.1 High concentrations of Fe cause spectral interference. 2. INTERFERENCES 3. Determination of boron 4. a coefficient of variation within 10 % + 10 mg/kg.1 End-over-end shaker. 5.B DETERMINATION OF BORON BY ICP-OES 1. where all components are vaporised.02 respectively 0.678 nm.4 Polythene volumetric flasks. Boron compounds are dissociated and excitated.5 Inductively coupled plasma optical emission spectrometer equipped with a polythene nebuliser.2 The detection limit is approximately 0.2 Polycarbonate test tubes.3 Polythene bottles. 2. 5.HCl).1 Solutions with boron compounds are nebulised into an argon plasma. 5.2 (extraction with HF . at reasonable control and thorough sample preparation.06 mg/kg in the dried plant material). APPARATUS 5.1 This procedure yields a standard curve that is linear up to at least 10 mg/L B. PRINCIPLE OF THE METHOD 1.44 Determinations. 4. 5. and then emit radiation of which the intensity is measured at a wavelength of 249. 3. 1. RANGE AND DETECTION LIMIT 2.

Na2B4O7.00 mL of the stock solution (6. Beryllium (5 mg/L). Wash twice with 15 mL water. At this wavelength a (fitted) background correction is used. (see remark 1) in some water in a 1000- mL volumetric flask and make up to volume. REAGENTS 6. PROCEDURE 8. B concentration 1000 mg/L .19500.0 – 10. then filter the newly formed crystals on a Büchner funnel by suction. This standard series has B concentrations of 0 – 5. 8.Measure in the standard series. the blanks and the sample extracts the B concentration with the ICP-OES at a wavelength of 249.1 The total boron content in the dried plant material. Remark: 2. CALIBRATION AND STANDARDS 7.861 nm. After the final washing.819 g of borax (sodium tetraborate decahydrate). 7. B concentration 1000 mg/L Dissolve 8. the solid has to be dried on a watch glass at room temperature for 12-18 h (Besset et al. Determination of boron 45 6. 15 mL ethanol and finally with 15 mL of diethyl ether. A mix standard series can be used for simultaneous measurements with ICP-OES (B and Si). Borax easily loses crystal water on standing. 1978). Remarks: 4.10H2O. 5. Laboratory coats fresh from the laundry might release boron (from the perborate used in washing powder). 9. Each washing must be followed by suction to remove the liquid.Pipette 0 – 0.1 Measurement . Let cool down and make up the mark with water. 3.2). To be sure that the salt contains 10 molecules of crystal water it has to be recrystallised. is used in the author's laboratory as an internal standard to compensate for matrix effects. expressed in mg/kg B.50 – 1. First dissolve 30 g borax in 100 mL water. is calculated by: (a .5 mL concentrated hydrochloric acid (36 %) (extraction 3.The emission counts are plot versus mg/L boron in the standard series.1 Standard Series . CALCULATION 9.Merck nr 1. 6.772 nm. 7.2 Calibration Curve .Determinations. Remark: 1.0 mg/L. at a wavelength of 234.b) * V / w .1B Stock Solution. The pipetting should be done by means of piston-type pipettes with polythene tips.1) into 100- mL polythene volumetric flasks which already contain 40 mL water and add 20 mL concentrated hydrofluoric acid (40 %) and 8.1A Stock Solution. Store in a polythene bottle.

10. in mL. 11: 83-84.46 Determinations. V is the total volume of digest at the end of the digestion procedure. Vogel's textbook of quantitative inorganic analysis. R. A new solvent extraction for the determination of traces of boron by ICP-AES. in mg/L. b is the concentration of boron in the blank digest. 300. and J. REFERENCES 10. V. I. London. 1990.1 Novozamsky.J.G. p. van Eck. Atomic Spectrosc. Determination of boron in which: a is the concentration of boron in the sample digest. J et al. 4th edition.2 Besset. in mg/L. w is the weight of plant material sample. van der Lee. Longman..J. . 10. 1978. in g. Houba.

the solubility product of CaSO4 can be surpassed in the digest. there may be interferences from P and Al. . 1.salicylic acid . a smaller sample has to be weighed out then. The determination limit is approximately 6 mg/L (7-25 mmol/kg in the dried plant material).H2O2 .2 (digestion with H2SO4 . by forming stable Ca2(PO4)3 and Ca2Al2O4 complexes in the flame.salicylic acid . digest 2.2 This determination may be carried out on digest 2. calcium compounds are atomised and the CaOH molecules thus formed emit radiation of which the intensity is measured at a wavelength of 622.2. INTERFERENCES 3. 3.H2O2 . where it is vaporised. PRINCIPLE OF THE METHOD 1.Se). whereas larger interferences at this wavelength only come from elements that hardly or not occur in plant material. Although Ca measurements are also possible at 423 nm and 554 nm.1 and 2.H2O2). 3. 2. 2.1 When using the cooler air-propane flame the emission signal is 30 .A DETERMINATION OF CALCIUM BY FLAME AES 1.4 (digestion with HNO3 - H2O2 .1 (digestion with H2SO4 . Determination of calcium 47 4.1 The sample is nebulised into an air-acetylene flame. 2. the spectral interferences at 622 nm are smaller for elements that are present in plant material. digest 2.Determinations.2 is higher than 1000 mmol/kg dry material.0 nm.4.HF).40 % lower.HF) and digest 2.3 (microwave digestion with HNO3 .4 DETERMINATION OF CALCIUM 4. and there will be more interferences.3 If the calcium content for digestion 2. RANGE AND DETECTION LIMIT 2. La can be used as a releasing agent to release Ca from the interfering compound.2 The detection limit is approximately 2 mg/L in the digest. When an air-acetylene flame is used. Remark: 1.7 (digestion by dry-ashing followed by treatment with HF). digest 2.1 This procedure yields a standard curve that is linear up to approximately 50 mg/L Ca.

because a lower quality (e. Allow to cool and make up to volume with water. Add 13 mL of 4 M hydrochloric acid (6. After the recommended heating procedure.Add 34 mL of concentrated hydrochloric acid (36 %) to about 400 mL water and make up to 1 litre. in a 1000-ml volumetric flask and make up to the mark with water.48 Determinations. The calcium carbonate has to be dried at 105 °C for at least 2 hours just before weighing. Remark: 2. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on. La(NO3)3. allow cooling in a desiccator). because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. Determination of calcium 4.1 Flame atomic emission spectrometer.43 g lanthanum nitrate hexahydrate. 6. and 3. La concentration 1. This is important.2) and boil to expel CO2.6H2O.1 g/L .Weigh out 2.3A Lanthanum Solution.1 g/L.3B Cesium-Lanthanum Solution.2) extra.2 Hydrochloric Acid 4 mol/L . 6. 3. La(NO3)3. REAGENTS 61A Stock Solution. the calcium carbonate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant.g. If calcium carbonate particles remain visible. . 6.19778. APPARATUS 5.4 g cesium chloride.Dissolve 3. Just before drying. PRECISION AND ACCURACY 4. 5.497 g of calcium carbonate. a coefficient of variation within 5 % + 5 mmol/kg.43 g lanthanum nitrate hexahydrate. however. The fine crystals should. CaCO3 (dried at 105 oC for 2 hours. 6. “reinst” = “most pure”) contains much more Na. Ca concentration 1000 mg/L . Cs concentration 1. Ca concentration 1000 mg/L . 6.6H2O. in a 1000-ml volumetric flask and make up to the mark with water. Transfer it to a 1000-mL volumetric flask with the help of about 150 mL water. The dried calcium carbonate should be weighed as soon as it has reached the ambient temperature. at reasonable control and thorough sample preparation. La concentration 1. any lumps should be cut down so that only fine crystals remain. add 1 mL of 4 M hydrochloric acid (6. The cesium chloride should be of the highest analytical grade (“pro analysi”).1 The reproducibility of determinations by this procedure should give.Merck nr 1.1 g/L - Dissolve 1. CsCl.1B Stock Solution.

02495 * (a . b is the concentration of calcium in the blank digest. 3.7). 8. Remark: 5.b) * V / w in which: a is the concentration of calcium in the sample digest.0 – 50. since glass filters are not selective enough.1 Dilute the standard series. in g. This standard series has Ca concentrations of 0 – 100 – 200 – 300 – 400 – 500 mg/L.0 – 40.15. Add either 4. w is the weight of plant material sample. a simple emission spectrometer ("flame photometer") may only be supplied with a so-called Ca filter.3). CALCULATION 9.11. V is the total volume of digest at the end of the digestion procedure.1 The calcium content of the dried plant material. A mix standard series can be used for simultaneous measurements with Flame-AES (Ca.A) or Na (see section 4.The emission counts are plot versus mg/L calcium in the standard series. the diluted blanks and the diluted sample digests the Ca concentration with flame AES at a wavelength of 622.0 – 30.0 mL concentrated nitric acid (65 %) (digestion 2. In this case Cs is necessary as an ionisation buffer for the determination of K (see section 4. in mg/L. CALIBRATION AND STANDARD SERIES 7.solution (6.1B) into 100-mL volumetric flasks which already contain 40 mL water.1 or 2.0 – 20. K and Na).Pipette 0 – 10. expressed in mmol/kg.3B) (see remark 3) and mix. Make sure that this is an interference filter.3A) or with cesium . Remark: 4. is calculated by: 0. Determination of calcium 49 7.0 nm.1A or 6.2).A). in mL. 7.4) or 1. 10 mL concentrated nitric acid (65 %) (digestion 2.2 Calibration Curve .1 Standard Series .5 mL concentrated sulphuric acid (96 %) (digestion 2.0 mL concentrated hydrochloric acid (36 %) (digestion 2. in mg/L. Let cool down and make up to the mark with water. the blanks and sample digests 1 + 9 (v/v) with lanthanum . Instead of indicating a wavelength. PROCEDURE 8. Measure in the diluted standard series.lanthanum solution (6.0 mL of the stock solution (6. 9.Determinations. using an air-acetylene flame. .

salicylic acid .1 (digestion with H2SO4 . 3.4 (digestion with HNO3 - H2O2 .1 The reproducibility of determinations by this procedure should give. INTERFERENCES 3. digest 2. the solubility product of CaSO4 can be surpassed in the digest.Merck nr 1. 4.1 The sample is nebulised into an air-acetylene flame. 6.2 This determination may be carried out on digest 2. APPARATUS 5. REAGENTS 6. a coefficient of variation within 5 % + 5 mmol/kg. 2. Determination of calcium 4. .H2O2).HF). calcium compounds are atomised and the calcium atoms thus formed absorb radiation from a hollow-cathode lamp.2 (digestion with H2SO4 .1 and 2. at reasonable control and thorough sample preparation.B DETERMINATION OF CALCIUM BY FLAME AAS 1.3 (microwave digestion with HNO3 . a smaller sample has to be weighed out then.50 Determinations.HF) and digest 2.H2O2 . 2. 5.1 Since Ca atoms are easily captured in the flame into poorly dissociating compounds (like oxides).1A Stock solution.1 Flame atomic absorption spectrophotometer. digest 2.3 If calcium contents for digestion 2. a releasing agent like lanthanum must be added.1 This procedure yields a standard curve that is linear up to approximately 5 mg/L Ca. PRECISION AND ACCURACY 4. PRINCIPLE OF THE METHOD 1.19778. Ca concentration 1000 mg/L . where it is vaporised.4. 2.7 (digestion by dry-ashing followed by treatment with HF). RANGE AND DETECTION LIMIT 2. 1. The absorbance is measured at a wavelength of 422.H2O2 . The determination limit is approximately 6 mg/L (7-25 mmol/kg in the dried plant material).7 nm.Se).salicylic acid .2 are higher than 1000 mmol/kg dry material. digest 2.2 The detection limit is approximately 2 mg/L in the digest.

Just before drying.2). 7. the blanks and the sample digests 1 + 19 (v/v) with lanthanum nitrate solution (6. The calcium carbonate has to be dried at 105 °C for at least 2 hours just before weighing.5 mL concentrated sulphuric acid (96 %) (digestion 2. La(NO3)3. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. any lumps should be cut down so that only fine crystals remain.7).2 Calibration Curve .00 – 8. Remark: 1.1 or 2. the calcium carbonate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. using a yellow (reducing) air-acetylene flame.1A or 6.00 mL of the stock solution (6. 7.3). CALIBRATION AND STANDARDS 7.0 mL concentrated hydrochloric acid (36 %) (digestion 2.1 Dilute the standard series. PROCEDURE 8. Allow to cool and make up to volume with water.6H2O. Add 13 mL of 4 M hydrochloric acid (6.Add 34 mL of concentrated hydrochloric acid (36 %) to about 400 mL water and make up to 1 litre. 6.1 Standard series .7 nm.2 Hydrochloric Acid 4 mol/L . add 1 mL of 4 M hydrochloric acid (6. This standard series has Ca concentrations of 0 – 20 – 40 – 60 – 80 – 100 mg/L.Weigh out 2.1B Stock solution.Determinations.2) extra. . 6. The fine crystals should. After the recommended heating procedure. The calibration curve should be linear by virtue of the releasing action of lanthanum.3 Lanthanum solution. Measure in the diluted standard series.00 – 4. Determination of calcium 51 6. Ca concentration 1000 mg/L . in some water and make up to 1 litre with water.2) and boil to expel CO2.00 – 6.Dissolve 3. This is important.1B) into 100-mL volumetric flasks which already contain 40 mL water.497 g of CaCO3 (dried at 105 oC for 2 hours. If calcium carbonate particles remain visible.4) or 1. La concentration 1 g/L . Remark: 2.12 g of lanthanum nitrate hexahydrate. 8.Pipette 0 – 2. 3.00 – 10. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on.0 mL concentrated nitric acid (65 %) (digestion 2. the diluted blanks and the diluted sample digests the Ca concentration with flame AAS at a wavelength of 422. The dried calcium carbonate should be weighed as soon as it has reached the ambient temperature.3) and mix. Let cool down and make up to the mark with water. 10 mL concentrated nitric acid (65 %) (digestion 2. however. Add either 4.The absorbance (A) is plot versus mg/L calcium in the standard series. allow cooling in a desiccator) and transfer it with 100-150 mL water to a 1-litre volumetric flask.

1 The calcium content of the dried plant material. Determination of calcium 9. CALCULATION 9. . b is the concentration of calcium in the blank digest.02495 * (a .b) * V / w in which: a is the concentration of calcium in the sample digest. expressed in mmol/kg Ca. V is the total volume of digest at the end of the digestion procedure. in mL. w is the weight of plant material sample. in mg/L. in mg/L. is calculated by: 0. in g.52 Determinations.

The determination limit is approximately 0.19778. APPARATUS 5.2 The detection limit is approximately 0. and then emit radiation of which the intensity is measured at a wavelength of 317. Determination of calcium 53 4.Weigh out 2.1 (digestion with H2SO4 .7 (digestion by dry-ashing followed by treatment with HF). INTERFERENCES 3. a coefficient of variation within 5 % + 5 mmol/kg. 6.4. at reasonable control and thorough sample preparation. PRINCIPLE OF THE METHOD 1. digest 2. 3. 6. digest 2.03 respectively 0. RANGE AND DETECTION LIMIT 2.1 Inductively coupled plasma optical emission spectrometer. 5.3 (microwave digestion with HNO3 .4 (digestion with HNO3 - H2O2 .2 This determination may be carried out on digest 2.1A Stock Solution.HF) and digest 2. REAGENTS 6.1 This procedure yields a standard curve that is linear up to at least 200 mg/L Ca. If calcium carbonate .2 (digestion with H2SO4 . Ca concentration 1000 mg/L . where all components are vaporised.1 No interferences are expected.HF).Merck nr 1.H2O2 . Ca concentration 1000 mg/L .salicylic acid . 1. PRECISION AND ACCURACY 4.Determinations.933 nm.1 The reproducibility of determinations by this procedure should give. Calcium compounds are dissociated and excited. 2.1B Stock solution.C DETERMINATION OF CALCIUM BY ICP-OES 1.1 mmol/kg in plant material). 2. Add 13 mL of 4 M hydrochloric acid (6.004 mg/L in the digest.497 g of CaCO3 (see remark 1) and transfer it with 100-150 mL water to a 1-litre volumetric flask. 4.Se).2) and boil to expel CO2. digest 2.1 Solutions with calcium compounds are nebulised into an argon plasma.H2O2).H2O2 .salicylic acid .012 mg/L (0.

Co. 3. Fe. any lumps should be cut down so that only fine crystals remain. The fine crystals should. P. Cr. PROCEDURE 8. Mg. the calcium carbonate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant.00 – 2. After the recommended heating procedure. The calcium carbonate has to be dried at 105 °C for at least 2 hours just before weighing.2). Allow to cool and make up to volume with water. K. Let cool down and make up to the mark with water. The dried calcium carbonate should be weighed as soon as it has reached the ambient temperature. This standard series has Ca concentrations of 0 – 10 – 20 – 200 mg/L. Na. Pb. at a wavelength of 313.00 – 20. Ca. 7. This is important.Measure in the standard series. 6.1 or 2. A data management system and system controller are used. A mix standard series can be used for simultaneous measurements with ICP-OES (Al.5 mL concentrated sulphuric acid (96 %) (digestion 2.The emission counts are plot versus mg/L calcium in the standard series. CALIBRATION AND STANDARDS 7.00 mL of the stock solution (6. S and Zn).7). Cu. Remark: 2. 8.933 nm.54 D eterminations.2 Hydrochloric Acid 4 mol/L . which already contain 40 mL water. In this way the measurements are checked continuously and the data output is in concentration units in the digests. Mn. 5. At this wavelength a (fitted) background correction is used. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on. Ni.Add 34 mL of concentrated hydrochloric acid (36 %) to about 400 mL water and make up to 1 litre. Beryllium (5 mg/L). Remark: 1.4) or 1. Just before drying. however.1B) into 100-mL volumetric flasks. add 1 mL of 4 M hydrochloric acid (6. Determination of calcium particles remain visible. the blanks and sample digests the Ca concentration with the ICP-OES at a wavelength of 317. 7. As a check all standards can be measured as samples. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series. 10 mL concentrated nitric acid (65 %) (digestion 2.2 Calibration Curve .1 Measurement . Remarks: 3. is used in the author's laboratory as an internal standard to compensate for matrix effects. Cd.107 nm.0 mL concentrated nitric acid (65 %) (digestion 2.2) extra.0 mL concentrated hydrochloric acid (36 %) (digestion 2.1 Standard series .Pipette 0 – 1. Add either 4.3). .1A or 6. 4.

expressed in mmol/kg Ca. V is the total volume of digest at the end of the digestion procedure. CALCULATION 9. Determination of calcium 55 9. is calculated by: 0. b is the concentration of calcium in the blank digest.1 The total calcium content in the dried plant material. in g. in mg/L. in mL.02495 * (a . in mg/L. w is the weight of plant material sample.Determinations. .b) * V / w in which: a is the concentration of calcium in the sample digest.

1. Cd concentration 1000 mg/L . 3.HClO4 .2 This determination may be carried out on digest 2.02 mg/L in the digest.19777. PRECISION AND ACCURACY 4.5.7 (digestion by dry-ashing followed by treatment with HF). The absorbance is measured at a wavelength of 228.H2O2 .5 DETERMINATION OF CADMIUM 4.1A Stock Solution.06 mg/L (3.0-7.2 The detection limit is approximately 0.HF).4 (digestion with HNO3 . 5. background correction is necessary (deuterium or Smith-Hieftje). RANGE AND DETECTION LIMIT 2. Determination of cadmium 4. 2.Merck nr 1.A DETERMINATION OF CADMIUM BY FLAME AAS 1. 6.1 To avoid interferences as much as possible.8 nm. The determination limit is approximately 0. APPARATUS 5.3 (microwave digestion with HNO3 . digest 2.6 (digestion with HNO3 . 2. where it is vaporised. cadmium compounds are atomised and the cadmium atoms thus formed absorb radiation from a hollow cathode lamp.H2O2 .H2SO4) and digest 2.5 mg/kg in dried plant material).1 The sample is nebulised into an air-acetylene flame. . PRINCIPLE OF THE METHOD 1. REAGENTS 6. using background correction.56 Determinations.1 The reproducibility of determinations by this procedure should give.8 mg/L Cd. digest 2.HF). a coefficient of variation within 5 % + 5 mg/kg. INTERFERENCES 3.1 Flame atomic absorption spectrophotometer with a device for correcting background absorption.1 This procedure yields a standard curve that is linear up to approximately 0. 4. at reasonable control and thorough sample preparation.

Remark: 1. using background correction.80 mg/L. in some water in a 1000-mL volumetric flask and make up to volume. Cd concentration 50 mg/L . in mg/L.The absorbance (A) is plot versus mg/L cadmium in the standard series.b) * V / w in which: a is the concentration of cadmium in the sample digest.10 – 0.20 – 0.1 Standard Series .Pipette 5. in mL.2) into 100-mL volumetric flasks. w is the weight of plant material sample. Cd concentration 1000 mg/L .0 mL stock solution (6. the blanks and the sample digests the Cd concentration with flame AAS at a wavelength of 228. Use scale expansion if necessary. Determination of cadmium 57 6. Remark: 2.40 – 0. .80 – 1.05 – 0. The reagent should be standardised by titration with EDTA at pH 10 with Eriochrome Black T as an indicator. This standard series has Cd concentrations of 0 – 0.4H2O may absorb water on standing. which already contain 40 mL water.4H2O.60 mL of the standard solution (6.20 – 1.45 mL concentrated sulphuric acid (96 %) (digestion 2.10 – 0.3). expressed in Pg/kg Cd.Pipette 0 – 0. Let cool down and make up to the mark with water.1 The total cadmium content in the dried plant material.1A or 6.20 – 0.1 Measurement .60 – 0.Determinations. V is the total volume of digest at the end of the digestion procedure.2 Standard Solution. In this case Smith-Hieftje background correction is necesserary.0 mL concentrated hydrochloric acid (36 %) (digestion 2.6) or 1. Cd(NO3)2. 0.7). 7.1B Stock Solution. PROCEDURE 8.40 – 0.1B) into a 100-mL volumetric flask and make up to volume.Dissolve 2. 8. 6. Cd(NO3)2. Samples with high iron content may give too low results when applying a deuterium background correction system (Van der Lee et al. Add either 10 mL concentrated nitric acid (65 %) (digestion 2. b is the concentration of cadmium in the blank digest. CALCULATION 9.4). 7..2 Calibration Curve . in mg/L. in g. is calculated by: 1000 * (a . 9.8 nm.Measure in the standard series. 1987). CALIBRATION AND STANDARDS 7. 3 mL concentrated nitric acid (65 %) (digestion 2.744 g cadmium nitrate tetrahydrate.

58 Determinations. 41: 388-390..J. Houba and I. Determination of cadmium 10. Background corrections in the determination of Cd and Pb by flame AAS in plant and soil samples with high Fe levels. REFERENCES 10. E. J.M. 1987. V. Novozamsky. .G.J.J. Spectrosc.1 Van der Lee. Appl. Temminghoff.

439 nm.3 (microwave digestion with HNO3 . 6. RANGE AND DETECTION LIMIT 2.H2O2 . 1. 2. digest 2. .7 (digestion by dry-ashing followed by treatment with HF).Dissolve 2.19777.4 (digestion with HNO3 .1 The reproducibility of determinations by this procedure should give. 5.002 mg/L in the digest.Merck nr 1.HClO4 . at reasonable control and thorough sample preparation.H2SO4) and digest 2. The determination limit is approximately 0. REAGENTS 6.1 Solutions with cadmium compounds are nebulised into an argon plasma. in some water in a 1000-mL volumetric flask and make up to volume.6 (digestion with HNO3 . 4. 3.2 This determination may be carried out on digest 2. Cd concentration 1000 mg/L . 2. PRECISION AND ACCURACY 4.HF).B DETERMINATION OF CADMIUM BY ICP-OES 1.HF). where all components are vaporised. PRINCIPLE OF THE METHOD 1. 6. INTERFERENCES 3.1 Inductively coupled plasma optical emission spectrometer.0 mg/kg in dried plant material). Cd concentration 1000 mg/L .2 The detection limit is approximately 0.7 respectively 2.4H2O. a coefficient of variation within 5 % + 5 mg/kg. and then emit radiation of which the intensity is measured at a wavelength of 214. Cadmium compounds are dissociated and excited.1 No interferences are expected.1B Stock Solution. APPARATUS 5. digest 2.006 mg/L (0.744 g cadmium nitrate tetrahydrate.1 This procedure yields a standard curve that is linear up to at least 2 mg/L Cd.1A Stock Solution.H2O2 .Determinations.5. Cd(NO3)2. Determination of cadmium 59 4.

Na.1B) and make up to volume with ultra pure water.Pipette 0 – 1. 7.1 Measurement . This standard series has Cd concentrations of 0 – 1. K. At this wavelength a (fitted) background correction is used. A mix standard series can be used for simultaneous measurements with ICP-OES (Al. 8. A data management system and system controller are used. 3.4H2O may absorb water on standing.1 Standard Series . CALCULATION 9. Mn.1 mL concentrated nitric acid (65 % s.7). expressed in mg/kg Cd. Cd concentration 100 mg/L . P.2) into 100-mL volumetric flasks which already contain 40 mL water. Pb. Cr. Scandium (5 mg/L). 6.0 mg/L. Mg. Let cool down and make up to the mark with water. S and Zn). Remarks: 3. Cd(NO3)2. Determination of cadmium Remark: 1. Ca. the blanks and the sample digests the Cd concentration with the ICP-OES at a wavelength of 214.1 The total cadmium content in the dried plant material.1A or 6. The reagent should be standardised by titration with EDTA at pH 10 with Eriochrome Black T as an indicator.00 – 2.00 mL of the standard solution (6.45 mL concentrated sulphuric acid (96 %) (digestion 2. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series.p. Cu.2 Standard Solution.) in a 100-mL polythene volumetric flask which already contains about 50 mL ultra pure water. 4. As a check all standards can be measured as samples.2 Calibration Curve . at a wavelength of 255.0 mL concentrated nitric acid (65 %) (digestion 2.Measure in the standard series. 7.3). Ni. Remark: 2. 5. Fe. Add either 10 mL concentrated nitric acid (65 %) (digestion 2. In this way the measurements are checked continuously and the data output is in concentration units in the digests. is calculated by: (a . CALIBRATION AND STANDARDS 7.439 nm. 0.60 Determinations. is used in the author's laboratory as an internal standard to compensate for matrix effects.0 mL concentrated hydrochloric acid (36 %) (digestion 2.Pipette 0.b) * V / w in which: . Cd.00 mL stock solution (6.6) or 1. 9.0 – 2. PROCEDURE 8.The emission counts are plot versus mg/L cadmium in the standard series.235 nm. Add 10. Co.4).

in mg/L. V is the total volume of digest at the end of the digestion procedure. b is the concentration of cadmium in the blank digest. w is the weight of plant material sample. in mL. in g. . in mg/L.Determinations. Determination of cadmium 61 a is the concentration of cadmium in the sample digest.

background correction is necessary (e. The cadmium atoms thus formed absorb radiation from a hollow cathode lamp. at reasonable control and thorough sample preparation.05 µg/L in the digest. APPARATUS 5.6 (digestion with HNO3 .1 This procedure yields a standard curve that is linear up to approximately 4 µg/L Cd. Determination of cadmium 4.8 nm.1 The reproducibility of determinations by this procedure should give.19777.HF). RANGE AND DETECTION LIMIT 2.2 This determination may be carried out on digest 2. . digest 2.1 Electrothermal atomisation (graphite furnace) atomic absorption spectrophotometer with a device for correcting background absorption. 5. 3. The absorbance is measured at a wavelength of 228. digest 2. INTERFERENCES 3.2 Polythene cups.C DETERMINATION OF CADMIUM BY ETA-AAS 1.1A Stock Solution.2 The detection limit is approximately 0. 6. The determination limit is approximately 0. ashed and vaporised by electrical heating in a graphite furnace.g.1 Cadmium ions in the digest are subsequently dried. Zeeman background correction). 1.4 (digestion with HNO3 .H2SO4) and digest 2.62 Determinations. 5. PRECISION AND ACCURACY 4.HClO4 .5. 2. PRINCIPLE OF THE METHOD 1. Cd concentration 1000 mg/L . REAGENTS 6.HF).7 (digestion by dry-ashing followed by treatment with HF).15 µg/L (7. 4.Merck nr 1.5-18 µg/kg in the dried plant material).H2O2 . 2.3 (microwave digestion with HNO3 .H2O2 . a coefficient of variation within 10 %.1 To avoid interferences as much as possible.

add 20 mL nitric acid solution (6.Determinations.) in a 100-mL polythene volumetric flask which already contains about 50 mL ultra pure water. This standard series has Cd concentrations of 0 – 0.Pipette 0 – 0.00 – 2.3) into 100-mL which already contain 40 mL ultra pure water. 3.6 Butanol.5 Matrix modifier.7). Palladium(II)chloride 0. 7. 7.2 Calibration Curve .5 – 1 – 2 – 3 – 4 µg/L.2 Standard Solution.00 – 3.00 mL stock solution (6. 6.0 mL concentrated nitric acid (65 %) (digestion 2.8 Propanol-2 Solution 5 % . Remark: 1.5 mL concentrated nitric acid (65 %) and heat to dissolve.1 mL concentrated nitric acid (65 % s.4). Cd concentration 1000 mg/L .20 g palladium(II) chloride in 0. Cd concentration 10 mg/L . Cd(NO3)2.45 mL concentrated sulphuric acid (96 %) (digestion 2. Determination of cadmium 63 6. Transfer the solution into a 100-mL volumetric flask.1B Stock Solution.4 Nitric Acid Solution 5 mol/L .Dilute 25 mL propanol-2 in some ultra pure water in a 500-mL volumetric flask and make up to volume.p.4H2O may absorb water on standing.2) and make up to volume with ultra pure water.The absorbance (A) is plot versus Pg/L cadmium in the standard series.1A or 6.4H2O.4) and make up to volume.00 mL standard solution (6.00 g triton-X in about 20 mL ultra pure water.0 mL concentrated hydrochloric acid (36 %) (digestion 2. 6. Heat till almost dry and transfer the solution into a 100-mL volumetric flask and make up to volume.2 % . Let cool down and dilute to volume. 6.Pipette 1.Dilute 34.50 – 1.Dissolve 2.7 mL concentrated nitric acid (65 %) in about 30 mL ultra pure water in a 100-mL volumetric flask. 6. Cd(NO3)2.744 g cadmium nitrate tetrahydrate. Add 1.3 Diluted Standard Solution.00 – 4. 0.1B) into a 100-mL volumetric flask and make up to volume. Cd concentration 100 µg/L . 6. .7 Acidified Triton-X 100 Solution 1 % . The reagent should be standardised by titration with EDTA at pH 10 with Eriochrome Black T as an indicator. Let cool down and make up to the mark with ultra pure water.3).Dissolve 1. in some ultra pure water in a 1000-mL volumetric flask and make up to volume.00 mL of the diluted standard solution (6.6) or 1.Dissolve 0.1 Standard Series .Pipette 0. 6. Add either 10 mL concentrated nitric acid (65 %) (digestion 2. CALIBRATION AND STANDARDS 7. 6.

00 mL of the standard series. Put standards. the blanks and sample digests into polythene cups that fit in the automatic sampler of the atomic absorption spectrophotometer. Clean all glassware by leaving it for one night in 4 mol/L HNO3.8 - 8 2200 3. Pyrolytically coated partition tubes are used in the author's laboratory. 3.Pipette 1.6) and mix. The measurements can be performed with any ETA-AAS system. an automatic sampler and a Zeeman-effect background correction system and for a matrix of 0. Parameters Cd Settings lamp current 5 mA wavelength 228. 5. The present method was worked out using a Varian SpectrAA-300 atomic absorption spectrometer equipped with a graphite tube atomiser.H2O2).8 nm in the atomisation phase (use background correction). The relative standard deviation should be less than 2 % for three replicates.0 Ar/H2 2 130 35. before use.0 Ar/H2 5 600 5. The sample volume which is injected is 20 µL and of the matrix modifier 5 µL. Butanol (0.7) and mix thoroughly with an electric mini-stirrer. .2 % palladium chloride in 5 % butanol (matrix modifier) is necessary.0 Ar 6 600 2. For the given temperature program the use of 0.1 Measurement . Pipette 1 mL of the matrix modifier (6.5) into another cup. Heat in a graphite furnace according to an appropriate time-temperature programme (see remarks 5 and 6). Measure the absorbance at 228. For other digestion procedures the temperature program should be optimised. Every sample should be measured at least three times and for calculation the mean can be used. 1990).05 mL) is added.0 Ar Ar = argon. Remarks: 2. Ar/H2 = 95 % argon and 5 % hydrogen The temperature program given here is for the digestion procedure 2.5 - 7 2200 0. blanks and sample digests in the appropriate place of the sampler. Clean the polythene cups by leaving them for one night in 1 mol/L HNO3.0 Ar/H2 3 600 25.64 Determinations. then rinse with ultra pure water and twice with ethanol 96 %. add 0. PROCEDURE 8.8 nm slit width 0.4 M HNO3 (see remark 7).4 (HNO3 . modifier.05 mL of butanol (6. The wash solution of the automatic sampler contains a 5 % propanol-2 solution (6. Allow to dry by leaving at room temperature in an inverted position. Add 0.0 - 9 2600 0. Determination of cadmium 8. to 1 mL of the Pd solution.05 mL of the acidified triton-X solution (6.HF .5 nm measurement mode peak area Temperature program Step Temp (°C) Time (s) Sheath gas 1 95 5. The operating parameters and temperature programme are given below. in order to achieve more reproducible drying conditions in the graphite atomiser (Temminghoff. 4.2 Ar 10 2600 3.0 Ar/H2 4 600 5.8) in order to lower its surface tension and to prevent growth of bacteria.

9. V is the total volume of digest at the end of the digestion procedure. b is the concentration of cadmium in the blank digest. w is the weight of plant material sample. Signal stabilisation in Electrothermal Atomisation Atomic Absorption Spectrometry by means of addition of butanol.b) * V / w in which: a is the concentration of cadmium in the sample digest. The temperatures mentioned are instrument settings instead of real temperature values. in mL. Spectrom. in g. Determination of cadmium 65 6. Anal. When using other instruments or matrix modifiers. such settings may differ even within two instruments of the same type and should be always checked out experimentally. in Pg/L. E. 5: 273.Determinations. 1990. J. is calculated by: (a . expressed in µg/kg Cd.J. the optimum temperature values to be set may differ from the values given above. At.1 Temminghoff. REFERENCES 10.1 The total cadmium content in the dried plant material. CALCULATION 9. . 10.M. in Pg/L.

744 cadmium nitrate tetrahydrate. Cd(NO3).4H2O. PRECISION AND ACCURACY 4. and quantified with a channel electron multiplier. 6.4 (digestion with HNO3 . Cd concentration 1000 mg/L .1 The reproducibility of determinations by this procedure should give.HF). REAGENTS 6.66 Determinations.003 µg/L in the digest. . 1. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer.02609. Make up to 1000 mL with ultra pure water.D DETERMINATION OF CADMIUM BY ICP-MS 1. 6.5.2 This determination may be carried out on digest 2. 2.1 Solutions with cadmium compounds are nebulised into an argon plasma.2 The detection limit is approximately 0.1B Stock Solution. in some ultra pure water in a volumetric flask of 1000 mL. 2. PRINCIPLE OF THE METHOD 1. sorted according to their mass-to-charge ratios.HF) and digest 2.1 Inductively coupled plasma mass spectrometer. Cd concentration 1000 mg/L .1 Since the isotope 114Sn has the same mass as 114 Cd a correction factor should be used if the solution contains Sn.3 (microwave digestion with HNO3 .1A Stock Solution. Determination of cadmium 4. 5. digest 2. Cadmium is determined at mass 114 amu.H2O2 . APPARATUS 5.H2O2 .7 (digestion by dry-ashing followed by treatment with HF). 3.Dissolve 2.010 µg/L (1-3 µg/kg in the dried plant material). INTERFERENCES 3. at reasonable control and thorough sample preparation. where all components are vaporised. RANGE AND DETECTION LIMIT 2.Merck nr 1.1 This procedure yields a standard curve that is linear up to at least 50 Pg/L Cd. The determination limit is approximately 0. a coefficient of variation within 10 %. 4.

Determinations.4H2O may absorb water on standing.00 mL of the standard solution (6. Remark: 1.1A or 6. CALCULATION 9. Sn. the blanks and the sample digests the Cd concentration with the ICP-MS at a mass of 114 amu. Remarks: 3.p.00 – 2. 7. Cd.b) * V / w in which: a is the concentration of cadmium in the sample digest. Cd concentration 1 mg/L . Cu. is calculated by: (a . in mL.The emission counts are plot versus Pg/L cadmium in the standard series. A mix standard series can be used for simultaneous measurements with ICP-MS (Al. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series.4) or 0. Ni.1 Standard Series .) in a 1000-mL polythene volumetric flask which already contains about 500 mL ultra pure water. V is the total volume of digest at the end of the digestion procedure. CALIBRATION AND STANDARDS 7.1 mL concentrated hydrochloric acid (36 %) (digestion 2.7). The reagent should be standardised by titration with EDTA at pH=10 with Eriochrome Black T as an indicator. As a check all standards can be measured as samples.1 The total cadmium content in the dried plant material. expressed in µg/kg Cd. Cd(NO3). Cr. Sb. A data management system and system controller are used. In this way the measurements are checked continuously and the data output is in concentration units in the digests. V and Zn). 8.2 Calibration Curve . 0.2 Standard Solution. Co. b is the concentration of cadmium in the blank digest. . Pb.pipette 0 – 1. Add 1. in g. 4.3 mL concentrated nitric acid (65 %) (digestion 2. As. in Pg/L. Let cool down and make up to the mark with ultra pure water. PROCEDURE 8.1 Measurement – Measure in the standard series. 9. Mn. w is the weight of plant material sample.0 mL concentrated nitric acid (65 %) (digestion 2. Remark: 2. in Pg/L.2) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks.1B) and make up to volume with ultra pure water. Add either 1. Determination of cadmium 67 6.Pipette 1 mL concentrated nitric acid (65 % s.00 – 5. This standard series has Cd concentrations of 0 – 10 – 20 – 50 µg/L.00 mL stock solution (6.3). 7.

silver. this current activates a trigger circuit to stop the pulse counter.5 mmol/L (25 mmol/kg in the dried plant material). Gelatin is added to the solution to keep the precipitate well suspended. The solution to be measured is acidified to allow a smooth reaction at the reference electrode. 1. PRECISION AND ACCURACY 4.1 Chloride is titrated with silver ions. 5.1 Coulometer.6 DETERMINATION OF CHLORIDE 4. fitted for titrations at constant current. The end point is detected by a sudden increase in current through a separate set of silver electrodes. In the present procedure. all newly generated silver ions come instantaneously into contact with the precipitate (see remark 7). The determination limit is approximately 0. which are generated from a silver anode at constant current. a coefficient of variation within 10 % + 10 mmol/kg. Determination of chloride 4. caused by the first excess of free silver ions.6.A DETERMINATION OF CHLORIDE BY COULOMETRIC TITRATION 1. Remarks: 1. 2. like phosphate and carbonate. and also to prevent adsorption of silver ions on the precipitate and to prevent the precipitation of other silver salts.1 The detection limit is approximately 0.68 Determinations. The total number of pulses counted is a direct measure of the amount of chloride in the sample. In that way. 2. INTERFERENCES 3. . RANGE AND DETECTION LIMIT 2. 4.1 The reproducibility of determinations by this procedure should give.15 mmol/L in the digest. at reasonable control and thorough sample preparation.1 No interferences are expected if only Cl free filters are used. In a coulometric titration at constant current. 3. 5. 3. the apparatus used is calibrated directly in millimoles of chloride. PRINCIPLE OF THE METHOD 1.2 Working electrode. APPARATUS 5.1 (extraction with water). the total quantity of electricity passed is derived from the product: current * time.2 This determination may be carried out on extract 3.

The procedure is written for the use of this particular instrument. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. this is a Dutch-made coulometer. heat on a water bath or in a beaker with hot water until the gelatin has dissolved. The sodium chloride has to be dried at 200 °C for at least 24 hours just before weighing. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on. Add 50 mL water and soak for 2 h at room temperature.Add 8 mL of concentrated nitric acid (65 %) in about 500 mL water in a 1000-mL volumetric flask. a so-called "Chlor-O-Counter" is used. Store in a refrigerator but do not freeze. Put into a 100-mL volumetric flask and add 10 mg of thymol (to prevent mould growth) and 10 mg of thymol blue and make up the mark. After the recommended heating procedure. but in principle any commercially available coulometer will serve the purpose. however. which is especially adapted for rapid chloride determinations.4 Gelatin Solution . 6. The fine crystals should. any lumps should be cut down so that only fine crystals remain.Pipette 10.2 Standard Solution.2) must be titrated to establish the actual relation. Only one standard solution (6. 6. Prepare fresh weekly. NaCl (see remark 5) in water in a volumetric flask of 1000 mL and make up to the mark. 5. In the authors' laboratory. 6. Then add 100 mL of concentrated acetic acid (100 %) and dilute to volume with water and mix.3 Acid Mixture . silver. This is important.Dissolve 5. Cl concentration 100 mmol/L .1 Stock Solution. Determination of chloride 69 5. Remark: 5. Just before drying. silver.1 Standard Series . 7.844 g of sodium chloride. The dried sodium chloride should be weighed as soon as it has reached the ambient temperature. CALIBRATION AND STANDARDS 7. Cl concentration 10 mmol/L . since the number of pulses (representing the total amount of electricity consumed) is directly proportional to the amount of chloride. 6. Thereafter.Determinations.3 Reference electrode.4 Detection electrodes.No standard series is needed.1) into a 100-mL volumetric flask and dilute to volume.0 mL of the stock solution (6.Weigh out 600 mg of gelatin (granules of purity grade "album") in a 100-mL beaker. REAGENTS 6. . Remark: 4. the sodium chloride should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant.

Remarks: 6. Put the counter to zero again.00 mL of the standard solution (6. 8. When less than 200 pulses per sample are counted.3) x 1 mL of gelatin solution (6. record the number of pulses (about 1000) and put the counter to zero again.2) into the same 50-mL beaker containing the previously titrated solution. Check also whether the generator electrode is still thick enough (at least 2 mm).1 Pretreatment of the Titration Medium .per pulse). very small: 1 mg for 1 mL of standard solution. press the key "titrating". Bring into a tall-shaped 50-mL beaker: x 20 mL of acid mixture (6. The consumption of silver is. Stir for a few seconds and then start the titration at position 5 (= 5 x 10-9 mol Cl. so that it indicates whether the titration medium is still acidic enough and also whether the gelatin solution is actually added.per pulse). 8. it is appropriate to empty the beaker partly and to . Stir for a few seconds and then start the titration at position 10 (= 10 x 10-9 mol Cl. The titration process can be followed by observing the pulse counter and the formation of precipitate. When the titration is finished. however. The silver anode slowly dissolves by forming silver chloride.70 Determinations. record the number of pulses.3 Measurement of Samples . containing the previously titrated solution. clean them with a cleaning powder and wipe with tissue paper. the measurement must be repeated with more sample (D mL). in particular the detection electrodes. Determination of chloride 8. By pressing the key "pipetting". the procedure has to be started again with a fresh titration medium (see remark 8).Pipette 1.00 mL of the blank or the extract into the same 50-mL beaker.per pulse). 8. Repeat this procedure two or three times and adjust the current in such a way that 1000 ± 20 pulses are counted. When the beaker has become completely filled after several titrations. if necessary.4) x 2 mL of standard solution (6. and proceed as before. the stirring is stopped and the counter is put to zero again. In that case. The titration medium must contain some precipitate of AgCl. Adjust the current at the highest possible value (here: position 80 = 80 x 10-9 mol Cl. the counter stops automatically. and press the pushbutton "mixing". When the beaker has become completely filled.2 Measurement of Standard Solution .Check whether both electrode couples are scrupulously clean. and immerse the electrodes and the stirrer. After a few seconds. When the titration is finished. 9. so that during the sample titration the precipitate is formed rapidly enough. the number of pulses needs not to be recorded. PROCEDURES 8. The thymol blue is red-coloured below pH 2.Pipette 1. 7. When the titration is finished. pipette the next sample into the same titration medium. The titration medium is now ready for the measurements.2) Place the beaker on the titration stand. the titration medium is normally still acidic enough.

10. V is the volume of extract used for the extraction procedure. or the counter begins to run irregularly.1 The chloride content of the dried plant material. 9. in mL. is calculated by: 0.Determinations. 20. where n = actual number of pulses for the standard solution. In case the precipitation starts with difficulty. p is the position of current generator in the Chlor-O-Counter (p = 5. a higher current value can be chosen.001 * (a . 10. 40 or 80) D is the volume of plant extract pipetted. in mL. about twenty samples can be handled before the titration medium is "exhausted" (see remark 9). w is the weight of plant material sample. the titration medium may have become "exhausted". For chloride determinations in plant extracts. Otherwise. in g. CALCULATION 9. a correction factor 1000/n must be applied. When high concentrations are expected. In this way. In the calculation formula it is assumed that the standard solution provides 1000 ± 20 pulses. b is the number of pulses counted in the blank extract. 11. the prescribed current of 6 mA is for most samples sufficient.b) * p / D * V / w in which: a is the number of pulses counted in the sample extract. . which means that the acid has been consumed by the reaction at the reference electrode. The procedure should then be started again with fresh titration medium. Determination of chloride 71 proceed with the next samples. expressed in mmol/kg Cl. Remark: 12.

1.HF). Determination of cobalt 4.HClO4 . PRINCIPLE OF THE METHOD 1.7 (digestion by dry-ashing followed by treatment with HF).) in a 100-mL polythene volumetric flask which already contains . digest 2.p. and then emit radiation of which the intensity is measured at a wavelength of 231.1 Solutions with cobalt compounds are nebulised into an argon plasma.Pipette 0.0 mg/kg in dried plant material).1 This procedure yields a standard curve that is linear up to at least 2 mg/L Co.6 (digestion with HNO3 . 6.1 Inductively coupled plasma optical emission spectrometer.Merck nr 1.HF).H2SO4) and digest 2.1 No interferences are expected.02614. RANGE AND DETECTION LIMIT 2. 6.2 Standard Solution. PRECISION AND ACCURACY 4.3 (microwave digestion with HNO3 .7 DETERMINATION OF COBALT 4.H2O2 . at reasonable control and thorough sample preparation.4 (digestion with HNO3 . where all components are vaporised.H2O2 .0 respectively 6. digest 2.72 Determinations. Co concentration 1000 mg/L .1 The reproducibility of determinations by this procedure should give.1 mL concentrated nitric acid (65 % s. Cobalt compounds are dissociated and excited. The determination limit is approximately 0. 4.006 mg/L in the digest. INTERFERENCES 3. 3.7. 2. 5. 2. Co concentration 100 mg/L . REAGENTS 6.2 This determination may be carried out on digest 2.018 mg/L (2.1 Stock Solution. APPARATUS 5.160 nm.2 The detection limit is approximately 0. a coefficient of variation within 5 % + 5 mg/kg.A DETERMINATION OF COBALT BY ICP-OES 1.

2 Calibration Curve . Add either 10 mL concentrated nitric acid (65 %) (digestion 2.0 – 2. V is the total volume of digest at the end of the digestion procedure. is calculated by: (a . K. In this way the measurements are checked continuously and the data output is in concentration units in the digests. 9. 0. Na. Cu. A data management system and system controller are used.3). Add 10. is used in the author's laboratory as an internal standard to compensate for matrix effects. Mn. P. A mix standard series can be used for simultaneous measurements with ICP-OES (Al. Ni. PROCEDURE 8. Determination of cobalt 73 about 50 mL ultra pure water.00 mL of the standard solution (6. Cr. Remark: 1. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series.Determinations.6) or 1. Ca.Pipette 0 – 1. Mg. in mg/L. expressed in mg/kg Co. Scandium (5 mg/L).Measure in the standard series.1 Standard Series .0 mL concentrated hydrochloric acid (36 %) (digestion 2. Remarks: 3.0 mL concentrated nitric acid (65 %) (digestion 2.b) * V / w in which: a is the concentration of cobalt in the sample digest.7). Cd. 8.00 mL stock solution (6. This standard series has Co concentrations of 0 – 1. 4. in mg/L.00 – 2.235 nm. 5. in g.The emission counts are plot versus mg/L cobalt in the standard series. Fe. in mL. 3. S and Zn).1) and make up to volume with ultra pure water. b is the concentration of cobalt in the blank digest.1 Measurement . 7. at a wavelength of 255. Co.2) into 100-mL volumetric flasks which already contain 40 mL water. the blanks and the sample digests the Co concentration with the ICP-OES at a wavelength of 231.0 mg/L.1 The total cobalt content in the dried plant material. 7. As a check all standards can be measured as samples. CALIBRATION AND STANDARDS 7. w is the weight of plant material sample.4).45 mL concentrated sulphuric acid (96 %) (digestion 2. Let cool down and make up to the mark with water. . CALCULATION 9. At this wavelength a (fitted) background correction is used.160 nm.

1. 5.H2O2 .2 The detection limit is approximately 0.006 µg/L (0. 2. 2.1 Stock Solution.HF) and digest 2. a coefficient of variation within 5 % + 5 Pg/kg. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer.3 (microwave digestion with HNO3 .p.1 This procedure yields a standard curve that is linear up to at least 50 Pg/L Co.2 Standard Solution. Determination of cobalt 4. 6. RANGE AND DETECTION LIMIT 2.02614. Co concentration 1000 mg/L .7 respectively 2 µg/kg in the dried plant material).H2O2 .7 (digestion by dry-ashing followed by treatment with HF).1 Solutions with cobalt compounds are nebulised into an argon plasma. 4. PRINCIPLE OF THE METHOD 1.7. at reasonable control and thorough sample preparation. 6. Cobalt is determined at mass 59 amu. 24Mg35Cl and 36Ar23Na due to mass overlap 59 with Co. 3. and quantified with a channel electron multiplier.Merck nr 1.B DETERMINATION OF COBALT BY ICP-MS 1.4 (digestion with HNO3 . INTERFERENCES 118 3.1 Inductively coupled plasma mass spectrometer.74 Determinations.) in a 1000-mL polythene volumetric flask which already contains about . digest 2.2 This determination may be carried out on digest 2. PRECISION AND ACCURACY 4. APPARATUS 5. sorted according to their mass-to-charge ratios. where all components are vaporised.HF).1 The reproducibility of determinations by this procedure should give.002 µg/L in the digest.1 Interferences are expected from Sn++. Co concentration 1 mg/L . The determination limit is approximately 0.Pipette 1 mL concentrated nitric acid (65 % s. REAGENTS 6.

Determinations; Determination of cobalt 75

500 mL ultra pure water. Add 1.00 mL stock solution (6.1) and make up to volume
with ultra pure water.

7. CALIBRATION AND STANDARDS

7.1 Standard Series - pipette 0 – 1.00 – 2.00 – 5.00 mL of the standard solution (6.2) in
about 40 mL ultra pure water in a 100-mL polythene volumetric flasks. Add either
1.0 mL concentrated nitric acid (65 %) (digestion 2.3), 0.3 mL concentrated nitric
acid (65 %) (digestion 2.4) or 0.1 mL concentrated hydrochloric acid (36 %)
(digestion 2.7). Let cool down and make up to the mark with ultra pure water. This
standard series has Co concentrations of 0 –10 – 20 – 50 µg/L.

7.2 Calibration Curve - The emission counts are plot versus Pg/L cobalt in the standard
series.

Remark:
1. A mix standard series can be used for simultaneous measurements with ICP-MS (Al, As, Cd,
Co, Cr, Cu, Mn, Ni, Pb, Sb, Sn, V and Zn).

8. PROCEDURE

8.1 Measurement – Measure in the standard series, the blanks and the sample digests
the Co concentration with the ICP-MS at a mass of 59 amu. Make use of
corrections if necessary.

Remarks:
2. A data management system and system controller are used. In this way the measurements
are checked continuously and the data output is in concentration units in the digests.
3. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest
and zero standard of the standard series. As a check all standards can be measured as
samples.

9. CALCULATION

9.1 The total cobalt content in the dried plant material, expressed in µg/kg Co, is
calculated by:
(a - b) * V / w
in which:
a is the concentration of cobalt in the sample digest, in Pg/L;
b is the concentration of cobalt in the blank digest, in Pg/L;
V is the total volume of digest at the end of the digestion procedure, in mL;
w is the weight of plant material sample, in g.

76 Determinations; Determination of chromium

4.8 DETERMINATION OF CHROMIUM

4.8.A DETERMINATION OF CHROMIUM BY ICP-OES

1. PRINCIPLE OF THE METHOD

1.1 Solutions with chromium compounds are nebulised into an argon plasma, where all
components are vaporised. Chromium compounds are dissociated and excited,
and then emit radiation of which the intensity is measured at a wavelength of
205.560 nm.

1.2 This determination may be carried out on digest 2.3 (microwave digestion with
HNO3 - H2O2 - HF), digest 2.4 (digestion with HNO3 - H2O2 - HF), digest 2.6
(digestion with HNO3 - HClO4 - H2SO4) and digest 2.7 (digestion by dry-ashing
followed by treatment with HF).

2. RANGE AND DETECTION LIMIT

2.1 This procedure yields a standard curve that is linear up to at least 2 mg/L Cr.

2.2 The detection limit is approximately 0.003 mg/L in the digest. The determination
limit is approximately 0.009 mg/L (0.9 respectively 2.7 mg/kg in dried plant
material).

3. INTERFERENCES

3.1 No interferences are expected.

4. PRECISION AND ACCURACY

4.1 The reproducibility of determinations by this procedure should give, at reasonable
control and thorough sample preparation, a coefficient of variation within 10 % + 5
mg/kg.

5. APPARATUS

5.1 Inductively coupled plasma optical emission spectrometer.

6. REAGENTS

6.1 Stock Solution, Cr concentration 1000 mg/L - Merck nr 1.02613.

6.2 Standard Solution, Cr concentration 100 mg/L - Pipette 0.1 mL concentrated nitric
acid (65 % s.p.) in a 100-mL polythene volumetric flask which already contains

Determinations; Determination of chromium 77

about 50 mL ultra pure water. Add 10.00 mL stock solution (6.1) and make up to
volume with ultra pure water.

7. CALIBRATION AND STANDARDS

7.1 Standard Series - Pipette 0 – 1.00 – 2.00 mL of the stock solution (6.1) into 100-mL
volumetric flasks which already contain 40 mL water. Add either 10 mL
concentrated nitric acid (65 %) (digestion 2.3), 3.0 mL concentrated nitric acid (65
%) (digestion 2.4), 0.45 mL concentrated sulphuric acid (96 %) (digestion 2.6) or
1.0 mL concentrated hydrochloric acid (36 %) (digestion 2.7). Let cool down and
make up to the mark with water. This standard series has Cr concentrations of 0 –
1.0 – 2.0 mg/L.

Remark:
1. A mix standard series can be used for simultaneous measurements with ICP-OES (Al, Ca,
Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, S and Zn).

7.2 Calibration Curve - The emission counts are plot versus mg/L chromium in the
standard series.

8. PROCEDURE

8.1 Measurement - Measure in the standard series, the blanks and the sample digests
the Cr concentration with the ICP-OES at a wavelength of 205.560 nm. At this
wavelength a (fitted) background correction is used.

Remarks:
3. A data management system and system controller are used. In this way the measurements
are checked continuously and the data output is in concentration units in the digests.
4. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the
highest and zero standard of the standard series. As a check all standards can be measured
as samples.
5. Scandium (5 mg/L), at a wavelength of 255.235 nm, is used in the author's laboratory as an
internal standard to compensate for matrix effects.

9. CALCULATION

9.1 The total chromium content in the dried plant material, expressed in mg/kg Cr, is
calculated by:
(a - b) * V / w
in which:
a is the concentration of chromium in the sample digest, in mg/L;
b is the concentration of chromium in the blank digest, in mg/L;
V is the total volume of digest at the end of the digestion procedure, in mL;
w is the weight of plant material sample, in g.

02613.1 This procedure yields a standard curve that is linear up to approximately 50 Pg/L Cr.03 µg/L (0.Pipette 1 mL concentrated nitric acid (65 % s.p. 1. sorted according to their mass-to-charge ratios and quantified with a channel electron multiplier. where all components are vaporised.) in a 1000-mL polythene volumetric flask which already contains about . a coefficient of variation within 15 %.Merck nr 1. 5.1 Stock Solution.H2O2 .B DETERMINATION OF CHROMIUM BY ICP-MS 1. The determination limit is approximately 0.HF) and digest 2.H2O2 .01 µg/L in the digests. PRECISION AND ACCURACY 4. Chromium is determined at mass 52 or 53 amu. and 35Cl16O1H molecules at mass 52Cr and of 37Cl16O and 36Ar16O1H molecules at mass 53Cr.3 respectively 1 µg/kg in the dried plant material). 6. REAGENTS 6. Cr concentration 1 mg/L . RANGE AND DETECTION LIMIT 2. APPARATUS 5. 2. 2.8.2 The detection limit is approximately 0. Determination of chromium 4.78 Determinations. digest 2. Cr concentration 1000 mg/L . INTERFERENCES 3.7 (digestion by dry-ashing followed by treatment with HF).4 (digestion with HNO3 .3 (microwave digestion with HNO3 .1 Interferences can be expected from 36Ar16O.2 This determination may be carried out on digest 2.2 Standard Solution. 6. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer.1 The reproducibility of determinations by this procedure should give.HF). PRINCIPLE OF THE METHOD 1. 3. at reasonable control and thorough sample preparation. 40Ar12C. 4.1 Solutions with chromium compounds are nebulised into an argon plasma.1 Inductively coupled plasma mass spectrometer.

Mn. 8. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series. in Pg/L.3). In this way the measurements are checked continuously and the data output is in concentration units in the digest. Co. A data management system and system controller are used.0 mL concentrated nitric acid (65 %) (digestion 2.00 – 2.2 Calibration Curve . Cd. V is the total volume of digest at the end of the digestion procedure.1) and make up to volume with ultra pure water. . Remark: 1.00 mL stock solution (6. 7. Ni. b is the concentration of chromium in the blank digest.The counts per second are plot versus Pg/L chromium in the standard series. 9.4) or 0. in mL.00 mL of the standard solution (6. CALCULATION 9.7).b) * V / w in which: a is the concentration of chromium in the sample digest. Sn.00 – 5. CALIBRATION AND STANDARDS 7. in Pg/L. V and Zn). Sb. Cu. 7.2) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks. Add 1. Pb.1 mL concentrated hydrochloric acid (36 %) (digestion 2. Add either 1.3 mL concentrated nitric acid (65 %) (digestion 2. 3. in g. is calculated by: (a . This standard series has Cr concentrations of 0 –10 – 20 – 50 µg/L.1 Standard Series . Remarks: 2.pipette 0 – 1. A mix standard series can be used for simultaneous measurements with ICP-MS (Al. w is the weight of plant material sample. As a check all standards can be measured as samples.1 The total chromium content in the dried plant material. As. 0. the blanks and the sample digests the Cr concentration with the ICP-MS at a mass of 52 amu. Cr. Determination of chromium 79 500 mL ultra pure water. Let cool down and make up to the mark with ultra pure water. PROCEDURE 8.1 Measurement – Measure in the standard series. expressed in µg/kg Cr.Determinations.

INTERFERENCES 3.2 The detection limit is approximately 0.A DETERMINATION OF COPPER BY FLAME AAS 1. 6.02 mg/L in the digest. 1. 6.3 (microwave digestion with HNO3 .2 This determination may be carried out on digest 2.1 No interferences are expected. Determination of copper 4.6 (digestion with HNO3 .929 g copper sulphate pentahydrate.9 DETERMINATION OF COPPER 4. The determination limit is approximately 0.HF). 5. where it is vaporised. digest 2. 4.1A Stock Solution.HF). at reasonable control and thorough sample preparation.4 (digestion with HNO3 .H2SO4) and digest 2. PRECISION AND ACCURACY 4. a coefficient of variation within 5 % + 5 mg/kg. REAGENTS 6. PRINCIPLE OF THE METHOD 1. Cu concentration 1000 mg/L . . 2.1 Flame atomic absorption spectrophotometer. 2.1 This procedure yields a standard curve that is linear up to approximately 4 mg/L Cu.Dissolve 3.1 The reproducibility of determinations by this procedure should give. APPARATUS 5.80 Determinations.H2O2 . The absorbance is measured at a wavelength of 324.9.7 (digestion by dry-ashing followed by treatment with HF).0-7.5 mg/kg in the dried plant material).HClO4 . 3. in about 500 mL water in a 1000-mL volumetric flask and make up to volume.Merck nr 1.06 mg/L (3. copper compounds are atomised and the copper atoms thus formed absorb radiation from a hollow cathode lamp.1B Stock Solution.1 The sample is nebulised into an air-acetylene flame. CuSO4. Cu concentration 1000 mg/L .19786.H2O2 .8 nm. RANGE AND DETECTION LIMIT 2.5H2O. digest 2.

Cu concentration 100 mg/L . CALIBRATION AND STANDARDS 7. using a just blue (stoichiometric) air-acetylene flame. in mg/L.25 – 0.0 mg/L. Determination of copper 81 6.8 nm.50 – 2. CALCULATION 9.b) * V / w in which: a is the concentration of copper in the sample digest.4). in mL.2 Standard Solution. b is the concentration of copper in the blank digest. Let cool down and make up to the mark with water. in mg/L.1 Measurement – Measure in the standard series. CuSO4.00 mL stock solution (6.0 mL concentrated nitric acid (65 %) (digestion 2. Remark: 1.2 Calibration Curve .7).0 mL concentrated hydrochloric acid (36 %) (digestion 2.50 – 1. expressed in mg/kg Cu. in g.45 mL concentrated sulphuric acid (96 %) (digestion 2.6) or 1.0 – 1.1B) into a 100-mL volumetric flask and make up to volume. the blanks and the sample digests the Cu concentration with flame AAS at a wavelength of 324.1 Standard Series . 3. 7.3). PROCEDURE 8.Determinations.1A or 6.25 – 0. This standard series has Cu concentrations of 0 – 0. . 7. 0.5H2O may lose crystal water on standing.1 The total copper content in dried plant material.5 – 2. w is the weight of plant material sample. 9.00 – 1. is calculated by: (a . Add either 10 mL concentrated nitric acid (65 %) (digestion 2. The reagent should be standardised by titration with EDTA at pH 10 with murexide as an indicator.00 mL of the standard solution (6. V is the total volume of digest at the end of the digestion procedure.Pipette 10.2) into 100-mL volumetric flasks which already contain 40 mL water.5 – 1. Use scale expansion if necessary.The absorbance (A) is plot versus mg/L copper in the standard series.Pipette 0 – 0. 8.

PRECISION AND ACCURACY 4. digest 2.7 (digestion by dry-ashing followed by treatment with HF). 5.1 This procedure yields a standard curve that is linear up to at least 2 mg/L Cu.2 This determination may be carried out on digest 2. at reasonable control and thorough sample preparation.3 (microwave digestion with HNO3 . 6. 6. PRINCIPLE OF THE METHOD 1.Dissolve 3. 3. a coefficient of variation within 5 % + 5 mg/kg. Copper compounds are dissociated and excited.HClO4 . Remark: . and then emit radiation of which the intensity is measured at a wavelength of 327. Cu concentration 1000 mg/L .1 No interferences are expected. digest 2.HF).395 nm.82 Determinations.929 g copper sulphate pentahydrate.1 The reproducibility of determinations by this procedure should give. in about 500 mL water in a 1000-mL volumetric flask and make up to volume.19786.1A Stock Solution. where all components are vaporised. The determination limit is approximately 0.B DETERMINATION OF COPPER BY ICP-OES 1. 2.HF).H2O2 . 1.0 mg/kg in the plant material). Cu concentration 1000 mg/L . APPARATUS 5. CuSO4.Merck nr 1.1B Stock Solution.1 Inductively coupled plasma optical emission spectrometer.009 mg/L (1. RANGE AND DETECTION LIMIT 2. INTERFERENCES 3.5H2O.6 (digestion with HNO3 .9.003 mg/L in the digest.1 Solutions with copper compounds are nebulised into an argon plasma. REAGENTS 6.0 respectively 3.H2O2 . Determination of copper 4.4 (digestion with HNO3 .2 The detection limit is approximately 0.H2SO4) and digest 2. 4. 2.

7). w is the weight of plant material sample. 5.00 – 2. Cu concentration 100 mg/L . P. Remarks: 3.1 mL concentrated nitric acid (65 % s.b) * V / w in which: a is the concentration of copper in the sample digest. K. Beryllium (5 mg/L). Cr.Determinations. CuSO4. Let cool down and make up to the mark with water.00 mL stock solution (6.3).0 mL concentrated nitric acid (65 %) (digestion 2. Ni. in g.107 nm. A mix standard series can be used for simultaneous measurements with ICP-OES (Al.2 Standard Solution. is calculated by: (a . 7. 7.1 Standard Series . As a check all standards can be measured as samples.395 nm.Measure in the standard series. in mg/L. Cu.1 Measurement . At this wavelength a (right side) background correction is used.2 Calibration Curve .) in a 100-mL polythene volumetric flask which already contains about 50 mL ultra pure water. Co. Na. in mg/L.6) or 1. b is the concentration of copper in the blank digest. A data management system and system controller are used. In this way the measurements are checked continuously and the data output is in concentration units in the digests. 6.Pipette 0. Add 10.1A or 6.The emission counts are plot versus mg/L copper in the standard series. expressed in mg/kg Cu. .0 – 2.1B) and make up to volume with ultra pure water. S and Zn). 9.1 The total copper content in the dried plant material.0 mL concentrated hydrochloric acid (36 %) (digestion 2. 8.4). Add either 10 mL concentrated nitric acid (65 %) (digestion 2. CALIBRATION AND STANDARDS 7. Mn. PROCEDURE 8. at a wavelength of 313. This standard series has Cu concentrations of 0 – 1. 0. CALCULATION 9. Cd. Fe.45 mL concentrated sulphuric acid (96 %) (digestion 2.p. 3.5H2O may lose crystal water on standing.0 mg/L.2) into 100-mL volumetric flasks which already contain 40 mL water. The reagent should be standardised by titration with EDTA at pH 10 with murexide as an indicator. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series. V is the total volume of digest at the end of the digestion procedure. 4. the blanks and the sample digests the Cu concentration with the ICP-OES at a wavelength of 327. Determination of copper 83 1.Pipette 0 – 1.00 mL of the standard solution (6. in mL. is used in the author's laboratory as an internal standard to compensate for matrix effects. Mg. Ca. Remark: 2.

4 (digestion with HNO3 . background correction is necessary (e. Zeeman background correction).1 Copper ions in the digest are subsequently dried.1 To avoid interferences as much as possible.HF). PRECISION AND ACCURACY 4.7 nm as wavelength for measurement.6 (digestion with HNO3 . 3. a coefficient of variation within 10 %.2 µg/L in the digest.4 nm an improved curve linearity.1 This procedure yields a standard curve that is linear up to approximately 50 µg/L Cu. . Determination of copper 4.3 (microwave digestion with HNO3 . 4. The absorbance is measured at a wavelength of 327.6 µg/L (0.H2O2 .HClO4 . RANGE AND DETECTION LIMIT 2.4 nm. the graphite furnace determination has at 327.C DETERMINATION OF COPPER BY ETA-AAS 1. Whereas the flame AAS determination normally uses 324. APPARATUS 5.2 This determination may be carried out on digest 2.4 respectively 1. 5.1 Electrothermal atomisation (graphite furnace) atomic absorption spectrophotometer with a device for correcting background absorption.H2SO4) and digest 2. 5. The determination limit is approximately 3. The copper atoms thus formed absorb radiation from a hollow cathode lamp.2 mg/kg in the dried plant material). Remark: 1.1 The reproducibility of determinations by this procedure should give. PRINCIPLE OF THE METHOD 1.HF) digest 2.2 The detection limit is approximately 1.g. INTERFERENCES 3. at reasonable control and thorough sample preparation. 2. digest 2. 1.2 Polythene cups.84 Determinations.H2O2 .7 (digestion by dry-ashing followed by treatment with HF).9. ashed and vaporised by electrical heating in a graphite furnace. 2.

The absorbance (A) is plot versus mg/L copper in the standard series.19786. Let cool down and dilute to volume.Dilute 25 mL propanol-2 in some ultra pure water in a 500-mL volumetric flask and make up to volume. Cu concentration 1000 mg/L .00 mL stock solution (6. 6.0 mL concentrated nitric acid (65 %) (digestion 2.6 Acidified Triton-X 100 Solution 1 % . CALIBRATION AND STANDARDS 7.1A Stock Solution. 6.5H2O.00 – 2. Transfer the solution into a 100-mL volumetric flask. 3. add 20 mL nitric acid solution (6. Remark: 2. 6.1A or 6.Dissolve 3. Determination of copper 85 6.Dissolve 0.Pipette 0 – 1.4 Matrix modifier. Add 1.Dilute 34.5H2O may lose crystal water on standing.5 mL concentrated nitric acid (65 %) and heat to dissolve. in about 500 mL ultra pure water in a 1000-mL volumetric flask and make up to volume.00 g triton-X in about 20 mL ultra pure water.2 Diluted Standard Solution. 6.p.7 mL concentrated nitric acid (65 %) in about 30 mL ultra pure water in a 100-mL volumetric flask. The reagent should be standardised by titration with EDTA at pH 10 with murexide as an indicator.1B Stock Solution. 6. 6.4).6) or 1.4) and make up to volume. 6. Cu concentration 1 mg/L . CuSO4.929 g copper sulphate pentahydrate.00 – 4.45 mL concentrated sulphuric acid (96 %) (digestion 2. Cu concentration 1000 mg/L .Pipette 1 mL concentrated nitric acid (65 % s. REAGENTS 6.2) into 100-mL volumetric flasks which already contain 40 mL of ultra pure water.3 Nitric Acid Solution 5 mol/L .00 mL of the diluted standard solution (6. Let cool down and make up to the mark with ultra pure water.00 – 3.) in a 1000-mL polythene volumetric flask which already contains about 500 mL ultra pure water.Merck nr 1.2 Calibration Curve . CuSO4.2 % . 7. .Determinations. 0. Palladium(II)chloride 0.3). This standard series has Cu concentrations of 0 – 10 – 20 – 30 – 40 – 50 µg/L. Heat till almost dry and transfer the solution into a 100-mL volumetric flask and make up to volume.20 g palladium(II) chloride in 0.00 – 5.7 Propanol-2 Solution 5 % .0 mL concentrated hydrochloric acid (36 %) (digestion 2. 7.5 Butanol.1B) and make up to volume with ultra pure water.1 Standard Series .Dissolve 1. Add either 10 mL concentrated nitric acid (65 %) (digestion 2.7).

00 mL of the standard series.0 Ar Ar = argon.1 Measurement .3 Ar 10 2500 3.0 Ar/H2 4 500 15. Heat in a graphite furnace according to an appropriate time-temperature programme (see remarks 5 and 6).5) and mix. The present method was worked out using a Varian SpectrAA-300 atomic absorption spectrometer equipped with a graphite tube atomiser. Pipette 1 mL of the matrix modifier (6. The relative standard deviation should be less than 2 % for three replicates.7) in order to lower its surface tension and to prevent growth of bacteria. The wash solution of the automatic sampler contains a 5 % propanol-2 solution (6.0 Ar/H2 5 500 5. PROCEDURE 8.5 - 7 2300 0. Remarks: 3. 4.HF .9 - 8 2300 3. 5. Add 0.0 Ar 6 500 2.4 nm slit width 0. The operating parameters and temperature programme are given below. modifier. The sample volume which is injected is 25 µL and of the matrix modifier 5 µL.4 nm in the atomisation phase (use background correction). blanks and sample digests in the appropriate place of the sampler. For using the given temperature program 0. Parameters Cu Settings Lamp current 4 mA Wavelength 327.4 M HNO3 (see remark 7).0 - 9 2500 0.86 Determinations. Determination of copper 8.H2O2).4 (HNO3 . Butanol (0.2 % palladium chloride in 5 % butanol as matrix modifier is necessary. Put standards. .Pipette 1.0 Ar/H2 2 130 35. add 0.05 mL of the acidified triton-X solution (6. before use. Ar/H2 = 95 % argon and 5 % hydrogen The temperature program given here is for the digestion procedure 2. to 1 mL of the Pd solution.6) and mix thoroughly with an electric mini-stirrer. in order to achieve more reproducible drying conditions in the graphite atomiser (Temminghoff. Pyrolytically coated partition tubes are used in the author's laboratory. an automatic sampler and a Zeeman-effect background correction system and for a matrix of 0.4) into another cup. the blanks and sample digests into polythene cups that fit in the automatic sampler of the atomic absorption spectrophotometer. 1990). For other digestion procedures the temperature program should be optimised. Measure the absorbance at 327. Every sample should be measured at least three times and for calculation the mean can be used.5 nm Measurement mode Peak area Replicates 3 Temperature program Step Temp (°C) Time (s) Sheath gas 1 95 5. The measurements can be performed with any ETA-AAS system.0 Ar 11 40 17.05 mL of butanol (6.05 mL) is added.0 Ar/H2 3 500 25.

expressed in mg/kg Cu. the optimum temperature values to be set may differ from the values given above. At. J. b is the concentration of copper in the blank digest.1 Temminghoff. V is the total volume of digest at the end of the digestion procedure. such settings may differ even within two instruments of the same type and should be always checked out experimentally. in g. The temperatures mentioned are instrument settings instead of real temperature values. Signal stabilisation in Electrothermal Atomisation Atomic Absorption Spectrometry by means of addition of butanol. in Pg/L. Spectrom.Determinations. When using other instruments or matrix modifiers. in Pg/L.001 * (a .M. w is the weight of plant material sample. 1990. CALCULATION 9. 10. 5: 273. REFERENCES 10. in mL. 9.J.1 The total copper content in the dried plant material. is calculated by: 0. .b) * V / w in which: a is the concentration of copper in the sample digest. Determination of copper 87 6. Anal. E.

1.HF).1A Stock Solution.02630. PRECISION AND ACCURACY 4.4 (digestion with HNO3 . 2. Cu concentration 1000 mg/L . 2. Cu concentration 1000 mg/L . 6. in some ultra pure water in a volumetric flask of 1000 mL. where all components are vaporised.88 Determinations. The determination limit is approximately 0. sorted according to their mass-to-charge ratios and quantified with a channel electron multiplier.1 This procedure yields a standard curve that is linear up to at least 50 Pg/L Cu. 4.1B Stock Solution. INTERFERENCES 3.1 The reproducibility of determinations by this procedure should give.1 Solutions with copper compounds are nebulised into an argon plasma.5H2O. 3. a coefficient of variation within 10 %. Make up to 1000 mL with ultra pure water.3 (microwave digestion with HNO3 .Dissolve 3.Merck nr 1.HClO4 . PRINCIPLE OF THE METHOD 1.H2O2 .7 (digestion by dry-ashing followed by treatment with HF). CuSO4.6 (digestion with HNO3 . RANGE AND DETECTION LIMIT 2. .929 g copper sulphate pentahydrate. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer.03 µg/L in the digest.1 No interferences are expected. 6.H2SO4) and digest 2. digest 2.HF).09 µg/L (10 respectively 30 µg/kg in the dried plant material). 5. Determination of copper 4.9. at reasonable control and thorough sample preparation.2 This determination may be carried out on digest 2.H2O2 . digest 2. Copper is determined at mass 63 amu. REAGENTS 6.2 The detection limit is approximately 0.D DETERMINATION OF COPPER BY ICP-MS 1.1 Inductively coupled plasma mass spectrometer. APPARATUS 5.

00 mL of the standard solution (6. Sb.1 Measurement – Measure in the standard series. 8. w is the weight of plant material sample. The reagent should be standardised by titration with EDTA at pH=10 with Murexide as an indicator. Cu.Determinations.0 mL concentrated nitric acid (65 %) (digestion 2. is calculated by: (a . 7. This standard series has Cu concentrations of 0 –10 – 20 – 50 µg/L. Add 1.7). As a check all standards can be measured as samples.1 The total copper content in the dried plant material.1 Standard Series .The counts per second are plot versus Pg/L copper in the standard series.5H2O may lose crystal water on standing. 0. A data management system and system controller are used. 0. Cu concentration 1 mg/L . As. expressed in µg/kg Cu. V is the total volume of digest at the end of the digestion procedure.2 Standard Solution. the blanks and the sample digests the Cu concentration with the ICP-MS at a mass of 63 amu. In this way the measurements are checked continuously and the data output is in concentration units in the digests. in mL. CALIBRATION AND STANDARDS 7.p. Cd.b) * V / w in which: a is the concentration of copper in the sample digest.1 mL concentrated hydrochloric acid (36 %) (digestion 2.045 mL concentrated sulphuric acid (96 %) (digestion 2.6) or 0. Cr. Add either 1. Sn. Co. Pb. in g. 4.00 – 5. in Pg/L. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series. A mix standard series can be used for simultaneous measurements with ICP-MS (Al.pipette 0 – 1. CALCULATION 9. 9. Remark: 1.3 mL concentrated nitric acid (65 %) (digestion 2. Remark: 2.00 mL stock solution (6.4). Let cool down and make up to the mark with ultra pure water. . PROCEDURE 8. in Pg/L.2) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks.3). Determination of copper 89 6.Pipette 1 mL concentrated nitric acid (65 % s.2 Calibration Curve . 7. Mn. Remarks: 3. b is the concentration of copper in the blank digest. Ni. V and Zn).1A or 6.00 – 2.) in a 1000-mL polythene volumetric flask which already contains about 500 mL ultra pure water.1B) and make up to volume with ultra pure water. CuSO4.

19781.HF). 2. at reasonable control and thorough sample preparation. a coefficient of variation within 5 % + 5 mg/kg.A DETERMINATION OF IRON BY FLAME AAS 1. in a 1000-mL volumetric flask which .10. 1. iron compounds are atomised and the iron atoms thus formed absorb radiation from a hollow-cathode lamp. 6.05 mg/L in the digest. RANGE AND DETECTION LIMIT 2. (NH4)2Fe(SO4)2. The absorbance is measured at a wavelength of 248. where it is vaporised. which is linear up to approximately 5 mg/L Fe.2 This determination may be carried out on digest 2. 5. 4.7 (digestion by dry-ashing followed by treatment with HF).1 Flame atomic absorption spectrophotometer. Fe concentration 1000 mg/L .6H2O. digest 2.1 This procedure yields a standard curve.HF). digest 2.6 (digestion with HNO3 .Merck nr 1.3 (microwave digestion with HNO3 .1 The reproducibility of determinations by this procedure should give.0170 g of ammonium iron sulphate hexahydrate. 6.H2O2 . APPARATUS 5. INTERFERENCES 3.Dissolve 7.4 (digestion with HNO3 . PRECISION AND ACCURACY 4.HClO4 . METHOD OF THE PRINCIPLE 1.1 The sample is nebulised into an air-acetylene flame.2 The detection limit is approximately 0.5-18 mg/kg in the dried plant material).90 Determinations.H2SO4) and digest 2. The determination limit is approximately 0.H2O2 .1B Stock Solution. REAGENTS 6.1 No interferences are expected.15 mg/L (7. Determination of iron 4.1A Stock Solution.3 nm.10 DETERMINATION OF IRON 4. 2. Fe concentration 1000 mg/L . 3.

Determinations.00 – 6.7). Determination of iron 91 contains already 200 mL water and 10 mL concentrated nitric acid (65 %).b) * V / w in which: a is the concentration of iron in the sample digest. in mg/L.00 – 10.2 Standard Solution Fe concentration 50 mg/L . expressed in mg/kg Fe. Add 1 mL concentrated nitric acid (65 %) and make up the mark with water. CALIBRATION AND STANDARDS 7.0 mL concentrated nitric acid (65 %) (digestion 2.2 Calibration Curve -The absorbance (A) is plot versus mg/L iron in the standard series.45 concentrated sulphuric acid (96 %) (digestion 2.4).3 nm. w is the weight of plant material sample. The reagent should be standardised by titration with EDTA at pH 2. . Let cool down and make up to the mark with water. 7. 8.00 – 8.1 Standard Series .00 mL of the standard solution (6. in g. the blanks and the sample digests the Fe concentration with flame AAS at a wavelength of 248.6) or 1. using a blue (oxidising) air-acetylene flame. in mg/L. b is the concentration of iron in the blank digest. 9.0 mL of the stock solution (6.1A or 6.6H2O may lose crystal water on standing. 3. in mL.1 The iron content of the dried plant material. 0.5 with sulfosalicylic acid as an indicator.1B) into a 500-mL volumetric flask. CALCULATION 9.2) into 100-mL volumetric flasks which already contain 40 mL water.Pipette 0 – 2. 7. Make up to the mark with water.00 – 4.3). 6. PROCEDURE 8. Add either 10 mL concentrated nitric acid (65 %) (digestion 2.Pipette 25. is calculated by: (a . Remark: 1. (NH4)2Fe(SO4)2. V is the total volume of digest at the end of the digestion procedure.0 mL concentrated hydrochloric acid (36 %) (digestion 2.1 Measure in the standard series. This standard series has Fe concentrations of 0 – 1 – 2 – 3 – 4 – 5 mg/L.

66 respectively 2. a coefficient of variation within 5 % + 5 mg/kg.HF).7 (digestion by dry-ashing followed by treatment with HF). Determination of iron 4.H2O2 .B DETERMINATION OF IRON BY ICP-OES 1. (NH4)2Fe(SO4)2.0 mg/kg in the dried plant material). RANGE AND DETECTION LIMIT 2.92 Determinations.Merck nr 1. 1.Dissolve 7.1 Solutions with iron compounds are nebulised into an argon plasma.1 No interferences are expected. Remark: .6H2O.06 mg/L (0.H2O2 . The determination limit is approximately 0.1 The reproducibility of determinations by this procedure should give.4 (digestion with HNO3 .0170 g ammonium iron sulphate hexahydrate.HClO4 . 2. Fe concentration 1000 mg/L . digest 2. 6.2 This determination may be carried out on digest 2. Make up to 1000 mL with water.HF). 4. 5. Fe concentration 1000 mg/L .3 (microwave digestion with HNO3 .94 nm. INTERFERENCES 3.10. 2.002 mg/L in the digest. Iron compounds are dissociated and excited.H2SO4) and digest 2. PRECISION AND ACCURACY 4.2 The detection limit is approximately 0.1A Stock Solution.19781. and then emit radiation of which the intensity is measured at a wavelength of 259.1 Inductively coupled plasma atomic emission spectrometer. PRINCIPLE OF THE METHOD 1. REAGENTS 6.1 This procedure yields a standard curve that is linear up to at least 100 mg/L Fe. digest 2. APPARATUS 5. 6.1B Stock Solution. in a volumetric flask of 1000 mL.6 (digestion with HNO3 . where all components are vaporised. 3. at reasonable control and thorough sample preparation.

w is the weight of plant material sample. in mg/L.00 – 2. Na.7).1 Standard Series .1A or 6.0 mL concentrated nitric acid (65 %) (digestion 2.4). Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series. . As a check all standards can be measured as samples. in g. S and Zn).00 – 10. PROCEDURE 8.b) * V / w in which: a is the concentration of iron in the sample digest. Add either 10 mL concentrated nitric acid (65 %) (digestion 2.00 mL of the standard solution (6.0 mL concentrated hydrochloric acid (36 %) (digestion 2. Co. Scandium (5 mg/L).2 Calibration Curve . Cr. 5. Remarks: 3. V is the total volume of digest at the end of the digestion procedure. CALCULATION 9. 3. Ni. the blanks and the sample digests the Fe concentration with the ICP-OES at a wavelength of 238. In this way the measurements are checked continuously and the data output is in concentration units in the digests. is calculated by: (a . expressed in mg/kg Fe. 7. at a wavelength of 255.1B) into 100-mL volumetric flasks which already contain 40 mL water. Cd. 0. b is the concentration of iron in the blank digest. Let cool down and make up to the mark with water.5 with sulfosalicylic acid as an indicator. 7. A mix standard series can be used for simultaneous measurements with ICP-OES (Al.Pipette 0 – 1. The reagent should be standardised by titration with EDTA at pH 2. 8.235 nm. Mn.45 mL concentrated sulphuric acid (96 %) (digestion 2. (NH4)2Fe(SO4)2.1 Measurement . P.3). This standard series has Fe concentrations of 0 – 10 – 20 – 100 mg/L.Measure in the standard series. Determination of iron 93 1. 4. Cu.204 nm. in mL. in mg/L. K. CALIBRATION AND STANDARDS 7.Determinations.6) or 1. is used in the author's laboratory as an internal standard to compensate for matrix effects. Mg.6H2O may lose crystal water on standing. Remark: 2. A data management system and system controller are used.The emission counts are plot versus mg/L iron in the standard series. 9. Ca.1 The total iron content in the dried plant material. At this wavelength a (fitted) background correction is used. Fe.

1 This procedure yields a standard curve that is linear up to approximately 50 mg/L K.H2O2 .1A Stock Solution. 2.5 nm. digest 2. APPARATUS 5. The potassium atoms thus formed emit radiation of which the intensity is measured at a wavelength of 766.2 This determination may be carried out on digest 2. . 6.11 DETERMINATION OF POTASSIUM 4.HF).HF) and digest 2.1 (digestion with H2SO4 .3 (microwave digestion with HNO3 . PRECISION AND ACCURACY 4. K concentration 5000 mg/L . 5.1 The sample is vaporised in an air-propane flame and the potassium compounds are atomised. digest 2.LPS Benelux 1289. PRINCIPLE OF THE METHOD 1.2 (digestion with H2SO4 .1 Flame atomic emission spectrometer. a coefficient of variation within 5 % + 5 mmol/kg.Se).1 The reproducibility of determinations by this procedure should give. INTERFERENCES 3.2 The detection limit is approximately 2 mg/L in the digest. at reasonable control and thorough sample preparation. The determination limit is approximately 6 mg/L (7.94 Determinations.11.salicylic acid .4 (digestion with HNO3 - H2O2 . cesium is added to act as an ionisation buffer. 3. 2. REAGENTS 6. Determination of potassium 4.1 To prevent ionisation interferences.7 (digestion by dry-ashing followed by treatment with HF). RANGE AND DETECTION LIMIT 2. 4. 1. digest 2.7-19 mmol/kg in the dried plant material).H2O2 .3000.salicylic acid .A DETERMINATION OF POTASSIUM BY FLAME AES 1.H2O2).

Let cool down and make up to the mark with water.1B Stock Solution.2B Cesium-Lanthanum Solution. Determination of potassium 95 6.6H2O. however. Remark: 1.2B) is necessary instead of cesium solution (see section 4. 3.5 mL concentrated sulphuric acid (96 %) (digestion 2.Determinations. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on.0 mL concentrated nitric acid (65 %) (digestion 2. La(NO3)3.1 g/L - Dissolve 1. La concentration 1. 7.1 Standard Series .00 – 10.1 g/L. the potassium chloride should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. This is important.A or 4.0 mL concentrated hydrochloric acid (36 %) (digestion 2.1B) into 100-mL volumetric flasks to about 40 mL water. CsCl. The cesium chloride should be of the highest analytical grade ("pro analysi").4 g cesium chloride. Cs concentration 1.00 mL of the standard solution (6.00 – 6. PROCEDURE .1 or 2. The standard series has K concentrations of 0 – 100 – 200 – 300 – 400 – 500 mg/L.2). Lanthanum is used as a releasing agent to release Ca from the interfering compounds. and 3.4) or 1. CALIBRATION AND STANDARDS 7. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature.1 g/L . CsCl. 2. KCl (see remark 1). 6.2A Cesium Solution.15.2 Calibration Curve .534 g potassium chloride.g. Add either 4. Remark: 4.4 g cesium chloride. Remark: 3.7). 10 mL concentrated nitric acid (65 %) (digestion 2.Dissolve 9. 6. K and Na).43 g lanthanum nitrate hexahydrate. In this case cesium-lanthanum solution (6. any lumps should be cut down so that only fine crystals remain.4. Cs concentration 1.Pipette 0 – 2. 7. A mix standard series can be used for simultaneous measurements with Flame-AES (Ca.A).The emission counts are plot versus mg/L potassium in the standard series.00 – 8.1A or 6. in some water in a 1000-mL volumetric flask and make up to the mark with water. After the recommended heating procedure. K concentration 5000 mg/L . "reinst" = "most pure") contains much more Na. The fine crystals should. Just before drying. The dried potassium chloride should be weighed as soon as it has reached the ambient temperature.Dissolve 1. 8. because a lower quality (e.3). The calibration curve should be nearly linear. The potassium chloride has to be dried at 200 ° C for at least 24 hours just before weighing.00 – 4. in a 1000-mL volumetric flask and make up to the mark with water. in a 1000-ml volumetric flask and make up to the mark with water.

Determination of potassium 8.2B) (see remark 2) and mix.1 The total potassium content in the dried plant material. is calculated by: 0. Instead of indicating a wavelength.5 nm.02558 * (a .Dilute standard series. b is the concentration of potassium in the blank digest. in mL. a simple emission spectrometer (‘flame photometer’) may only be supplied with a so-called K filter. CALCULATION 9. Remarks: 5.96 Determinations. blanks and sample digests 1+9 (v/v) with the cesium solution or cesium-lanthanum solution (6. in mg/L. V is the total volume of digest at the end of the digestion procedure. Make sure that these are interference filters.2A or 6. w is the weight of plant material sample. since the Cs concentration is high enough to counteract the greater tendency to ionisation. 6.1 Measurement . 9. expressed in mmol/kg K. . using an air-propane flame. Measure in the diluted standard series.b) * V / w in which: a is the concentration of potassium in the sample digest. the diluted blanks and the diluted sample digests the K concentration with flame AES at a wavelength of 766. in g. An air-acetylene flame can be used also. since glass filters are not selective enough. in mg/L.

6. 6.3 (microwave digestion with HNO3 .1 (digestion with H2SO4 . INTERFERENCES 3.2 The detection limit is approximately 0.salicylic acid .2 mmol/kg in the dried plant material).19505. The potassium chloride has to be dried at 200 °C for at least 24 hours just before weighing.1A Stock Solution. PRINCIPLE OF THE METHOD 1.4 respectively 1. digest 2.Determinations. where all components are vaporised. at reasonable control and thorough sample preparation.Dissolve 1.14 mg/L (0. This is . APPARATUS 5. 2.B DETERMINATION OF POTASSIUM BY ICP-OES 1.1B Stock Solution. 4. Determination of potassium 97 4.1 This procedure yields a standard curve that is linear up to at least 20 mg/L K.4 (digestion with HNO3 - H2O2 .salicylic acid . K concentration 1000 mg/L .05 mg/L in the digest.9068 g potassium chloride. 5.1 Solutions with potassium compounds are nebulised into an argon plasma.11.491 nm.H2O2). 1. KCl (see remark 1).7 (digestion by dry-ashing followed by treatment with HF). a coefficient of variation within 5 %.H2O2 .2 This determination may be carried out on digest 2. digest 2.H2O2 .1 The reproducibility of determinations by this procedure should give. PRECISION AND ACCURACY 4. REAGENTS 6. Remark: 1. Potassium compounds are dissociated and excited. 3. Just before drying.HF). digest 2.1 Inductively coupled plasma optical emission spectrometer.2 (digestion with H2SO4 . and then emit radiation of which the intensity is measured at a wavelength of 766.Se). K concentration 1000 mg/L . in some water in a 1000-mL volumetric flask and make up to the mark with water.Merck nr 1. RANGE AND DETECTION LIMIT 2. 2.HF) and digest 2.1 No interferences are expected. The determination limit is approximately 0. any lumps should be cut down so that only fine crystals remain.

in g. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series. 9.Measure in the standard series.7). as an internal standard to compensate for matrix effects.2). This standard series has K concentrations of 0 – 10 – 20 mg/L. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on.1A or 6.00 mL of the stock solution (6. Remark: 2. Cd. at a wavelength of 431. expressed in mmol/kg K. After the recommended heating procedure. in mg/L. Determination of potassium important.98 Determinations. A data management system and system controller are used. however. w is the weight of plant material sample.5 mL concentrated sulphuric acid (96 %) (digestion 2. S and Zn). P. In this way the measurements are checked continuously and the data output is in concentration units in the digests. Mg.2 Calibration Curve .1 The total potassium content in the dried plant material.491 nm. 7. Mn.1 or 2. At this wavelength a (fitted) background correction is used.0 mL concentrated nitric acid (65 %) (digestion 2. Fe. Let cool down and make up to the mark with water. in mL.3). Ni.408 nm. 5. V is the total volume of digest at the end of the digestion procedure. Na. CALIBRATION AND STANDARDS 7. the blanks and the sample digests the K concentration with the ICP-OES at a wavelength of 766. 8. A mix standard series can be used for simultaneous measurements with ICP-OES (Al. Add either 4. Ca. Cu. K.Pipette 0 – 1. 3. 7. The dried potassium chloride should be weighed as soon as it has reached the ambient temperature.The emission counts are plot versus mg/L potassium in the standard series. 4. The fine crystals should.02558 * (a . PROCEDURE 8.1 Measurement .1B) into 100-mL volumetric flasks which already contain 40 mL water. b is the concentration of potassium in the blank digest. As a check all standards can be measured as samples. in mg/L. is calculated by: 0. Scandium (5 mg/L) is used in the author's laboratory. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature.1 Standard Series . 10 mL concentrated nitric acid (65 %) (digestion 2. the potassium chloride should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. Remarks: 3.b) * V / w in which: a is the concentration of potassium in the sample digest. . CALCULATION 9.00 – 2.0 mL concentrated hydrochloric acid (36 %) (digestion 2.4) or 1.

7 (digestion by dry-ashing followed by treatment with HF).H2O2 .1 The reproducibility of determinations by this procedure should give.4 (digestion with HNO3 - H2O2 .3 (microwave digestion with HNO3 .salicylic acid .12. 3. RANGE AND DETECTION LIMIT 2. digest 2. PRECISION AND ACCURACY 4.HF) and digest 2. INTERFERENCES 3. . 4. 5.2 nm.Determinations.2 (digestion with H2SO4 . a coefficient of variation within 7 % + 5 mmol/kg.2 This determination may be carried out on digest 2.5 mg/L Mg.A DETERMINATION OF MAGNESIUM BY FLAME AAS 1.Se).1 The sample is vaporised in an air-acetylene flame. PRINCIPLE OF THE METHOD 1. 2.2 The detection limit is approximately 0.HF).12 DETERMINATION OF MAGNESIUM 4. 2. digest 2. The absorbance is measured at a wavelength of 285. Determination of magnesium 99 4. in particular with phosphate and aluminium. magnesium compounds are atomised and the magnesium atoms thus formed absorb radiation from a hollow cathode lamp. at reasonable control and thorough sample preparation. APPARATUS 5.1 Since Mg atoms are easily captured in the flame into poorly dissociating compounds.H2O2). The determination limit is approximately 2. 1.1 This procedure yields a standard curve that is linear up to approximately 0.1 Flame atomic absorption spectrophotometer.salicylic acid .8 mg/L in the digest. digest 2.1 (digestion with H2SO4 .4 mg/L (5-16 mmol/kg in the dried plant material). a releasing agent like lanthanum must be added.H2O2 .

Dissolve 3. 3.1A or 6. in some water in a 1000-mL volumetric flask. the diluted blanks and the diluted sample digests the Mg concentration with flame AAS at a wavelength of 285.1B) in a 100-mL volumetric flask and make up to volume with water.0 mL stock solution (6. The reagent should be standardised by titration with EDTA at pH 10 with Eriochrome Black T as an indicator. MgSO4.3 Lanthanum Solution.3) into 100-mL volumetric flasks.1B Stock Solution. Remark: 2.Dissolve 10. Mg concentration 1000 mg/L .00 – 4.12 g lanthanum nitrate hexahydrate.00 – 8. 6. water. 8.3) and mix.100 Determinations. using a just blue (stoichiometric) air- acetylene flame.3).The absorbance (A) is plot versus mg/L magnesium in the standard series. This standard series has Mg concentrations of 0 – 10 – 20 – 30 – 40 mg/L.19788.2 Standard Solution.4) or 1.1 Standard Series . Mg concentration 500 mg/L . 7.0 mL concentrated hydrochloric acid (36 %) (digestion 2. 6.Pipette 0 – 2. 7.130 g magnesium sulphate heptahydrate.2 Calibration Curve . Remark: 1.1A Stock Solution.Merck nr 1.0 mL concentrated nitric acid (65 %) (digestion 2.Pipette 50. The calibration curve is slightly bent towards the x-axis. Mg concentration 1000 mg/L . MgSO4. Determination of magnesium 6. La(NO3)3.7H2O. Add either 4.6H2O.1 or 2. which contain already 40 mL.1 Measurement .7H2O may lose crystal water on standing. REAGENTS 6. .Dilute the standard series. 6.2 nm. CALIBRATION AND STANDARDS 7. PROCEDURE 8.2). La concentration 1 g/L . In that case calculation by means of linear regression is not allowed.00 mL of the standard solution (6.5 mL concentrated sulphuric acid (96 %) (digestion 2. Let cool down and make up to the mark with water.7). the blanks and the sample digests 1+39 (v/v) with the lanthanum solution (6. 10 mL concentrated nitric acid (65 %) (digestion 2.00 – 6. in some water in a 1000-mL volumetric flask and make up to the mark with water. Measure in the diluted standard series.

w is the weight of plant material sample.Determinations. . b is the concentration of magnesium in the blank digest. expressed in mmol/kg Mg.b) * V / w in which: a is the concentration of magnesium in the sample digest. in g. in mg/L.04114 * (a .1 The total magnesium content of the dried plant material. in mg/L. Determination of magnesium 101 9. CALCULATION 9. in mL. is calculated by: 0. V is the total volume of digest at the end of the digestion procedure.

270 nm. APPARATUS 5.1 This procedure yields a standard curve that is linear up to at least 40 mg/L Mg. PRINCIPLE OF THE METHOD 1.102 Determinations.Se). where all components are vaporised.2 This determination may be carried out on digest 2.HF).7H2O.Dissolve 10. digest 2.19788.H2O2). Determination of magnesium 4.130 g magnesium sulphate heptahydrate.2 (digestion with H2SO4 .1 Solutions with magnesium compounds are nebulised into an argon plasma.salicylic acid . 2. RANGE AND DETECTION LIMIT 2.003 mg/L (0. 5. PRECISION AND ACCURACY 4. Mg concentration 1000 mg/L .1 (digestion with H2SO4 .001 mg/L in the digest. digest 2. a coefficient of variation within 8 % + 5 mmol/kg.Merck nr 1. and then emit radiation of which the intensity is measured at a wavelength of 280. REAGENTS 6. 3.1A Stock Solution.1 No interferences are expected.salicylic acid . .04 mmol/kg in the dried plant material). INTERFERENCES 3.2 The detection limit is approximately 0.01 respectively 0. 2.H2O2 .B DETERMINATION OF MAGNESIUM BY ICP-OES 1. Mg concentration 1000 mg/L .3 (microwave digestion with HNO3 . Magnesium compounds are dissociated and excited.1 The reproducibility of determinations by this procedure should give.1B Stock Solution.12.H2O2 .7 (digestion by dry-ashing followed by treatment with HF). at reasonable control and thorough sample preparation. The determination limit is approximately 0. 6. in some water in a 1000-mL volumetric flask and make up to the mark with water. 1. 4. digest 2. MgSO4.HF) and digest 2.4 (digestion with HNO3 - H2O2 .1 Inductively coupled plasma optical emission spectrometer. 6.

Determinations; Determination of magnesium 103

Remark:
1. MgSO4.7H2O may lose crystal water on standing. The reagent should be standardised by
titration with EDTA at pH 10 with Eriochrome Black T as an indicator.

7. CALIBRATION AND STANDARDS

7.1 Standard Series - Pipette 0 – 1.00 – 2.00 – 4.00 mL of the standard solution (6.1A
or 6.1B) into 100-mL volumetric flasks which already contain 40 mL water. Add
either 4.5 mL concentrated sulphuric acid (96 %) (digestion 2.1 or 2.2), 10 mL
concentrated nitric acid (65 %) (digestion 2.3), 3.0 mL concentrated nitric acid (65
%) (digestion 2.4) or 1.0 mL concentrated hydrochloric acid (36 %) (digestion 2.7).
Let cool down and make up to the mark with water. This standard series has Mg
concentrations of 0 – 10 – 20 – 40 mg/L.

Remark:
2. A mix standard series can be used for simultaneous measurements with ICP-OES (Al, Ca,
Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, S and Zn).

7.2 Calibration Curve - The emission counts are plot versus mg/L magnesium in the
standard series.

8. PROCEDURE

8.1 Measurement - Measure in the standard series, the blanks and the sample digests
the Mg concentration with the ICP-OES at a wavelength of 280.270 nm. At this
wavelength a (fitted) background correction is used.

Remarks:
3. A data management system and system controller are used. In this way the measurements
are checked continuously and the data output is in concentration units in the digests.
4. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the
highest and zero standard of the standard series. As a check all standards can be measured
as samples.
5. Beryllium (5 mg/L), at a wavelength of 313.107 nm, is used in the author's laboratory as an
internal standard to compensate for matrix effects.

9. CALCULATION

9.1 The total magnesium content in the dried plant material, expressed in mmol/kg Mg,
is calculated by:
0.04114 * (a - b) * V / w
in which:
a is the concentration of magnesium in the sample digest, in mg/L;
b is the concentration of magnesium in the blank digest, in mg/L;
V is the total volume of digest at the end of the digestion procedure, in mL;
w is the weight of plant material sample, in g.

104 Determinations; Determination of manganese

4.13 DETERMINATION OF MANGANESE

4.13.A DETERMINATION OF MANGANESE BY FLAME AAS

1. PRINCIPLE OF THE METHOD

1.1 The sample is nebulised into an air-acetylene flame, where it is vaporised;
manganese compounds are atomised and the manganese atoms thus formed
absorb radiation from a hollow cathode lamp. The absorbance is measured at a
wavelength of 279.5 nm.

1.2 This determination may be carried out on digest 2.1 (digestion with H2SO4 - salicylic
acid - H2O2 - Se), digest 2.2 (digestion with H2SO4 - salicylic acid - H2O2), digest 2.3
(microwave digestion with HNO3 - H2O2 - HF), digest 2.4 (digestion with HNO3 -
H2O2 - HF), digest 2.6 (digestion with HNO3 - HClO4 - H2SO4) and digest 2.7
(digestion by dry-ashing followed by treatment with HF).

2. RANGE AND DETECTION LIMIT

2.1 This procedure yields a standard curve that is linear up to approximately 3 mg/L
Mn.

2.2 The detection limit is approximately 0.02 mg/L in the digest. The determination limit
is approximately 0.06 mg/L (3-10 mg/kg in the dried plant material).

3. INTERFERENCES

3.1 Lanthanum is added to prevent condensed phase interferences.

4. PRECISION AND ACCURACY

4.1 The reproducibility of determinations by this procedure should give, at reasonable
control and thorough sample preparation, a coefficient of variation within 5 % + 5
mg/kg.

5. APPARATUS

5.1 Flame atomic absorption spectrophotometer.

6. REAGENTS

6.1A Stock Solution, Mn concentration 1000 mg/L - Merck nr 1.19789.

6.1B Stock Solution, Mn concentration 1000 mg/L - Dissolve 2.877 g potassium
permanganate, KMnO4, in about 200 mL water in a beaker and add 1 mL

Determinations; Determination of manganese 105

concentrated nitric acid. Reduce the permanganate with a few drops of hydrogen
peroxide (30 %) and boil to remove the excess of H2O2. Transfer the contents of
the beaker quantitatively to a 1000-mL volumetric flask and make up to the mark.

6.2 Standard Solution, Mn concentration 100 mg/L - Pipette 10.00 mL stock solution
(6.1A or 6.1B) into a 100-mL volumetric flask and make up to the mark with water.

6.3 Lanthanum Solution, La concentration 16.5 g/L - Dissolve 12.86 g lanthanum
nitrate hexahydrate, La(NO3)3.6H2O, in some water in a 250-mL volumetric flask.

Remark:
1. KMnO4 may decompose on standing by influence of light. The reagent should be
standardised, after reduction with hydroxylamine-HCl, by titration with EDTA at pH 10 in the
presence of tartrate ions with Eriochrome Black T as an indicator.

7. CALIBRATION AND STANDARDS

7.1 Standard Series - Pipette 0 – 1.00 – 2.00 – 3.00 – 4.00 – 5.00 mL of the standard
solution (6.2) into 100-mL volumetric flasks to about to about 40 mL water. Add
either 4.5 mL concentrated sulphuric acid (96 %) (digestion 2.1 or 2.2), 10 mL
concentrated nitric acid (65 %) (digestion 2.3), 3.0 mL concentrated nitric acid (65
%) (digestion 2.4), 0.45 mL concentrated sulphuric acid (96 %) (digestion 2.6) or
1.0 mL concentrated hydrochloric acid (36 %) (digestion 2.7). Let cool down and
make up to the mark with water. This standard series has Mn concentrations of 0 –
1 – 2 – 3 – 4 – 5 mg/L.

7.2 Calibration Curve - The absorbance (A) is plot versus mg/L manganese in the
standard series.

Remark:
2. The calibration curve is slightly bent towards the x-axis. In that case calculation by means of
linear regression is not allowed.

8. PROCEDURE

8.1 Measurement - Pipette 5.00 mL of the standard series, the blanks and the sample
digests into test tubes. Add 0.50 mL of lanthanum solution (6.3) and mix. Measure
in the diluted standard series, the diluted blanks and the diluted sample digest the
Mn concentration with flame AAS at a wavelength of 279.5 nm, using a blue
(oxidising) air-acetylene flame.

9. CALCULATION

9.1 The total manganese content in the dried plant material, expressed in mg/kg Mn, is
calculated by:
(a - b) * V / w
in which:

106 Determinations. Determination of manganese a is the concentration of manganese in the sample digest. in mL. w is the weight of plant material sample. b is the concentration of manganese in the blank digest. . in mg/L. in g. in mg/L. V is the total volume of digest at the end of the digestion procedure.

APPARATUS 5.2 This determination may be carried out on digest 2.1 Inductively coupled plasma optical emission spectrometer. digest 2.1 The reproducibility of determinations by this procedure should give. 6. The determination limit is approximately 0.Determinations. 4.610 nm. 2. at reasonable control and thorough sample preparation.001 mg/L in the digest.Merck nr 1.13.H2O2 .1 This procedure yields a standard curve that is linear up to at least 2 mg/L Mn.1 No interferences are expected. Manganese compounds are dissociated and excited.4 (digestion with HNO3 - H2O2 . Determination of manganese 107 4. where all components are vaporised. PRECISION AND ACCURACY 4. 5.Se). 3.3 (microwave digestion with HNO3 .H2O2 .B DETERMINATION OF MANGANESE BY ICP-OES 1.2 The detection limit is approximately 0.19789.HClO4 . digest 2.HF).salicylic acid . digest 2. digest 2. Mn concentration 1000 mg/L .2 (digestion with H2SO4 .7 (digestion by dry-ashing followed by treatment with HF). REAGENTS 6. PRINCIPLE OF THE METHOD 1. a coefficient of variation within 5 % + 5 mg/kg.003 mg/L (0. and then emit radiation of which the intensity is measured at a wavelength of 257.6 (digestion with HNO3 . 2.salicylic acid .1A Stock Solution. 1.H2SO4) and digest 2.H2O2). .HF).1 Solutions with manganese compounds are nebulised into an argon plasma. RANGE AND DETECTION LIMIT 2. INTERFERENCES 3.3 respectively 1.1 (digestion with H2SO4 .0 mg/kg in the dried plant material).

00 – 2.1B Stock Solution.0 mg/L. Remarks: 3. Ni. 4. A data management system and system controller are used. Let cool down and make up to the mark with water.7).1 Standard Series . 10 mL concentrated nitric acid (65 %) (digestion 2. 6.5 mL concentrated sulphuric acid (96 %) (digestion 2. K. Mn.00 mL of the standard solution (6. Mg. Fe.1 or 2.2) into 100-mL volumetric flasks which already contain 40 mL water. 5. Remark: 2.1A or 6. The reagent should be standardised. As a check all standards can be measured as samples. CALIBRATION AND STANDARDS 7. P. Cd. Cu. by titration with EDTA at pH 10 in the presence of tartrate ions with Eriochrome Black T as an indicator. At this wavelength a (fitted) background correction is used.610 nm. 0. KMnO4 may decompose on standing by influence of light.2 Standard Solution. Mn concentration 100 mg/L .108 Determinations. Add either 4. Cr. after reduction with hydroxylamine-HCl. Ca.2 Calibration Curve .Pipette 0 – 1. KMnO4. at a wavelength of 255. Remark: 1.1 Measurement . in about 200 mL water in a beaker and add 1 mL concentrated nitric acid.0 mL concentrated hydrochloric acid (36 %) (digestion 2. Determination of manganese 6. In this way the measurements are checked continuously and the data output is in concentration units in the extracts.1B) in a 100-mL volumetric flask and make up to volume with water. is used in the author's laboratory as an internal standard to compensate for matrix effects. Na.Pipette 10.45 mL concentrated sulphuric acid (96 %) (digestion 2. .877 g potassium permanganate.00 mL stock solution (6. Transfer the contents of the beaker quantitatively to a 1000-mL volumetric flask and make up to the mark.3). 7. A mix standard series can be used for simultaneous measurements with ICP-OES (Al.The emission counts are plot versus mg/L manganese in the standard series.Measure in the standard series. 8. This standard series has Mn concentrations of 0 – 1.6) or 1. 3. Scandium (5 mg/L). Co. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series.Dissolve 2.4). S and Zn).2). PROCEDURE 8. 7.0 – 2.235 nm. Mn concentration 1000 mg/L . Reduce the permanganate with a few drops of hydrogen peroxide (30 %) and boil to remove the excess of H2O2.0 mL concentrated nitric acid (65 %) (digestion 2. the blanks and the sample digests the Mn concentration with the ICP-OES at a wavelength of 257.

Determination of manganese 109 9. expressed in mg/kg Mn. b is the concentration of manganese in the blank digest. in mg/L. is calculated by: (a . . in g.b) * V / w in which: a is the concentration of manganese in the sample digest. w is the weight of plant material sample.Determinations. in mL. CALCULATION 9. V is the total volume of digest at the end of the digestion procedure. in mg/L.1 The total manganese content in the dried plant material.

4.H2O2 . KMnO4. Reduce the permanganate with a few drops of hydrogen . and quantified with a channel electron multiplier. PRECISION AND ACCURACY 4.014 Pg/L in the digest. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer. Mn concentration 1000 mg/L . 39K16O and 23Na32S due to mass overlap with 55Mn. PRINCIPLE OF THE METHOD 1. in about 200 mL water in a beaker and add 1 mL concentrated nitric acid.877 g potassium permanganate.1 Interferences are expected from 40Ar14N1H.1 The reproducibility of determinations by this procedure should give. INTERFERENCES 3. sorted according to their mass-to-charge ratios. 2. The determination limit is approximately 0.HF). Mn concentration 1000 mg/L . digest 2.19789.4 (digestion with HNO3 . a coefficient of variation within 10 %.1 Inductively coupled plasma mass spectrometer. Manganese is determined at mass 55 amu. 5. RANGE AND DETECTION LIMIT 2. at reasonable control and thorough sample preparation.110 Determinations.2 The detection limit is approximately 0. 3.Merck nr 1. 6.1B Stock Solution.HF).6 (digestion with HNO3 .13.1 Solutions with manganese compounds are nebulised into an argon plasma.2 This determination may be carried out on digest 2. Determination of manganese 4. 2. APPARATUS 5.1A Stock Solution. REAGENTS 6. 1.H2SO4) and digest 2.3 (microwave digestion with HNO3 .7 (digestion by dry-ashing followed by treatment with HF). where all components are vaporised.042 Pg/L (5 respectively 14 µg/kg in the dried plant material).HClO4 .Dissolve 2. digest 2.H2O2 .1 This procedure yields a standard curve that is linear up to at least 50 Pg/L Mn.C DETERMINATION OF MANGANESE BY ICP-MS 1. 6.

1A or 6.3) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks.00 mL of the standard solution (6. As. Remarks: 3. KMnO4 may decompose on standing by influence of light. Determination of manganese 111 peroxide (30 %) and boil to remove the excess of H2O2. CALCULATION 9.3). is calculated by: (a . PROCEDURE 8.Determinations. The reagent should be standardised. 4.pipette 0 – 1. A data management system and system controller are used.1B) in a 1000-mL volumetric flask and make up to volume with ultra pure water. Sn.045 mL concentrated sulphuric acid (96 %) (digestion 2.) in a 1000-mL polythene volumetric flask which already contains about 500 mL ultra pure water.1 The manganese content of the dried plant material. expressed in µg/kg Mn. Make use of corrections if necessary.00 – 5.Pipette 1 mL concentrated nitric acid (65 % s. This standard series has Mn concentrations of 0 –10 – 20 – 50 µg/L. Add 1. CALIBRATION AND STANDARDS 7.3 mL concentrated nitric acid (65 %) (digestion 2. 7. A mix standard series can be used for simultaneous measurements with ICP-MS (Al.1 mL concentrated hydrochloric acid (36 %) (digestion 2. 7.7).00 mL stock solution (6. Let cool down and make up to the mark with ultra pure water. by titration with EDTA at pH 10 in the presence of tartrate ions with Eriochrome Black T as an indicator. 6. 9.0 mL concentrated nitric acid (65 %) (digestion 2. Remark: 2. 0. Cr. 8.1 Measurement – Measure in the standard series. As a check all standards can be measured as samples.p. Transfer the contents of the beaker quantitatively to a 1000-mL volumetric flask and make up to the mark. Sb.2 Calibration Curve . V and Zn). Mn. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series.b) * V / w . Cd.6) or 0. Co. the blanks and the sample digests the Mn concentration with the ICP-MS at a mass of 55 amu. Add either 1. Cu. 0. after reduction with hydroxylamine-HCl. Remark: 1. Pb.00 – 2. In this way the measurements are checked continuously and the data output is in concentration units in the digests.The counts per second are plot versus Pg/L manganese in the standard series.2 Standard Solution. Mn concentration 1 mg/L .4). Ni.1 Standard Series .

in Pg/L. Determination of manganese in which: a is the concentration of manganese in the sample digest. b is the concentration of manganese in the blank digest. in g.112 Determinations. in Pg/L. V is the total volume of digest at the end of the digestion procedure. . in mL. w is the weight of plant material sample.

1. To prevent precipitation of hydroxides. RANGE AND DETECTION LIMIT 2.1 Spectrophotometer.1 (digestion with H2SO4 . 2. the indophenol thus formed has a green-blue colour.salicylic acid . Determination of nitrogen fractions 113 4.1 The determination is based on the Berthelot reaction.H2O2-Se) and digest 2.A DETERMINATION OF TOTAL NITROGEN BY SPECTROPHOTOMETRY 1.2 This determination may be carried out on digest 2.1 mg/L in the digest. EDTA should be added prior to raising the pH. The determination limit is approximately 0. PRECISION AND ACCURACY 4. since the digests contain variable amounts of acid. at reasonable control and thorough sample preparation.salicylic acid . Remarks: 1.1 No interferences are expected.2 (digestion with H2SO4 .Determinations.1 This procedure yields a standard curve that is linear up to approximately 15 mg/L N.1 The reproducibility of determinations by this procedure should give. 4. of which the absorbance is measured at a wavelength of 660 nm. a coefficient of variation within 5 % + 5 mmol/kg. . PRINCIPLE OF THE METHOD 1. APPARATUS 5. formed by the nitrogen compounds in the sample. 2. 2. The pH should be adjusted with a buffer solution. Sodium nitroprusside is a catalyst for the Berthelot reaction.14.5 mmol/kg in the dried plant material). 5. in which a phenol derivative (here: salicylate) forms an azo dye in the presence of ammonia and hypochlorite. This is a measure for the concentration of ammonium. 3.3 mg/L (1.2 The detection limit is approximately 0.2 respectively 3. In alkaline medium.14 DETERMINATION OF NITROGEN FRACTIONS 4. INTERFERENCES 3. 3.H2O2).

2H2O. (NH4)2SO4 (see remark 4).7) and 5 mL of the EDTA solution (6.3 .3) with 100 mL of the nitroprusside solution (6.114 Determinations. Determination of nitrogen fractions 6. 6. 5.2H2O.5). because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature.4 Buffer Solution pH 12. This is important.7 Nitroprusside Solution . in 100 mL water. Na2HPO4. any lumps should be cut down so that only fine crystals remain.1 % of active chlorine.A stock solution.8 Mixed Reagent I .70 g of disodium hydrogen phosphate dihydrate. Prepare fresh daily.2H2O. 6.Dissolve 110 g of salicylic acid. however.Dissolve 50 mg of sodium nitroprusside dihydrate.1 Stock Solution. This will be true for solutions purchased from a supplier of chemicals. 6. After the recommended heating procedure. Prepare just before use. The ammonium sulphate has to be dried at 105 °C for at least 2 hours just before weighing. in about 400 mL water. The final solution of sodium hypochlorite should contain 0.Dissolve 4 g of disodium dihydrogen ethylene diamine tetra acetate dihydrate. 6. 6. 6. the hypochlorite was bought as bleach in a supermarket. allow to cool and make up to 500 mL.Dissolve 11.9 Mixed Reagent II . in some water in a 2-litre volumetric flask. should be purchased commercially. Add 10 mL of the sodium hydroxide solution (6. N concentration 2500 mg/L . a check on its concentration is recommended. Na2EDTA. Dilute 20 mL of this stock solution with water to 100 mL.7 % ± 0. The dried ammonium sulphate should be weighed as soon as it has reached the ambient temperature.1 M NaOH.5 EDTA Solution .6).793 g of ammonium sulphate. Just before drying. the ammonium sulphate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. 6. NaOH. C7H6O3.2) and dilute to volume with water. in water in a 1000-mL volumetric flask and make up to volume with water. Measure the pH and adjust if necessary. .2 Sodium Hydroxide Solution 10 mol/L . containing approximately 1 M sodium hypochlorite in 0.Mix 200 mL of the buffer solution (6.4) with 50 mL of the hypochlorite solution (6. however.3 Salicylate Solution .Dissolve 200 g of sodium hydroxide.Dissolve 26.Mix 50 mL of the salicylate solution (6. Na2[Fe(CN)5NO]. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on.6 Hypochlorite Solution . Remark: 4. The fine crystals should. 6.2) and make up directly with water to 250 mL. in 105 mL of sodium hydroxide solution (6. in 100 mL water. Prepare just before use. REAGENTS 6. if.

00 – 6. . 7.8) and mix. This standard series has N concentrations of 0 – 25 – 50 – 75 – 100 – 125 – 150 mg/L. 8.0 mL of mixed reagent II (6. 1974. 10. CALIBRATION AND STANDARDS 7.20 mL of the diluted standard series.agric. R.1 Dilute the standard series.1 Standard Series .Sci.07139 * (a . 4.J. it is stable for at least 10 h. expressed in mmol/kg N. Plot a calibration curve.1) and dilute to volume with water.00 – 5. the blanks and sample digests 1 + 9 (v/v) with water. 8.00 – 2.00 – 4.9 M in H2SO4. CALCULATION 9. Neth. Any further dilutions (if the N concentrations would be higher than the highest standard) should be made with zero standard solution.1 The nitrogen content of the dried plant material.5 mL of concentrated sulphuric acid (96 %).2 Calibration Curve .1 Novozamsky.7 . van Eck. I. The test tubes must be used exclusively for this N determination.0. In 2 hours the blue colour reaches its maximum intensity. J.9) and mix. PROCEDURE 8. Mix and let cool down. in mg/L. Then add 0 – 1.0 mL of mixed reagent I (6. Then add 5.b) V / w in which: a is the concentration of nitrogen in the sample digest. van Schouwenburg and I.00 mL of the stock solution (6. in g. Determination of nitrogen fractions 115 7. 22: 3-5.Determinations.The absorbance (A) is plot versus mg/L nitrogen in the standard series. REFERENCES 10. in mL. b is the concentration of nitrogen in the blank digest. Remarks: 6. Measure the absorbance in a 1-cm cuvette at a wavelength of 660 nm. 7. thereafter they should be cleaned only with water. Walinga. Add 3. They must first be cleaned by taking a blank determination. Total nitrogen determination in plant material by means of the indophenol blue method. in mg/L. the diluted blank digests and the diluted sample digests into test tubes.Ch. The digests obtained according to digestion 2.. and read the N concentrations.1 or 2. Pipette 0.2 are 0. w is the weight of plant material sample. 9. V is the total volume of digest at the end of the digestion procedure.00 – 3. is calculated by: 0. Allow standing for at least 2 h. that contain already about 40 mL water.Pipette into 100-mL volumetric flasks.

but any SFA system will do.1 This procedure yields a standard curve that is linear up to approximately 300 mg/L N. PRINCIPLE OF THE METHOD 1.2 respectively 3. a coefficient of variation within 5 % + 5 mmol/kg.2 (digestion with H2SO4 .Dissolve 38. This is a measure for the concentration of ammonium. in which a phenol derivative (here: salicylate) forms an azo dye in the presence of ammonia and hypochlorite. 3. in a 1000-mL volumetric flask which already contains about 800 mL water and make up to volume. .5 mmol/kg in the dried plant material).1 The reproducibility of determinations by this procedure should give.1 (digestion with H2SO4 .salicylic acid . The determination is carried out as a so-called segmented-flow analysis (SFA). The determination limit is approximately 0.salicylic acid . photometer.19 g ammonium chloride.14.1 Stock Solution 10000 mg/L N . 5. In alkaline medium.2 This determination may be carried out on digest 2. Determination of nitrogen fractions 4. In the authors' laboratory. that with other systems the flow diagram may require adaptation.H2O2).1 Segmented-flow analysis system (sampler.1 The determination is based on the Berthelot reaction.H2O2 . 4. 6. nitrogen unit. at reasonable control and thorough sample preparation. 2. RANGE AND DETECTION LIMIT 2.3 mg/L (1.2 The detection limit is approximately 0. of which the absorbance is measured at a wavelength of 660 nm. pump. 2.1 No interferences are expected.Se) and digest 2. Note. the indophenol thus formed has a green-blue colour.116 Determinations. INTERFERENCES 3.B DETERMINATION OF TOTAL NITROGEN BY SFA 1.1 mg/L in the digest. a Skalar Segmented Flow Analyzer is used. computer). 1. PRECISION AND ACCURACY 4. REAGENTS 6. formed by the nitrogen compounds in the sample. APPARATUS 5. NH4Cl (see remark 1).

The standard series has N concentrations of 0 – 100 – 200 – 300 mg/L.00 mL of the stock solution (6.1.3 Sodium Salicylate . Add 3 mL Brij 35 (30 %) (Sigma Chemical Co. however.4 Sodium Nitroprusside .00 – 3. C6H5O7Na3.1) and make up to volume with water. in a volumetric flask which already contains about 800 mL water and make up to volume and mix. The ammonium chloride has to be dried at 200 °C for at least 24 hours just before weighing.2 Buffer Solution.5 mL concentrated sulphuric acid (96 %) (digestion 2.2 Calibration Curve . which already contains about 800 mL water.5 Rinsing Liquid Sampler . Determination of nitrogen fractions 117 6.Pipette into a 100-mL volumetric flasks which already contain 40 mL water 4. Add 80 g sodium salicylate. C4H4O6KNa. the ammonium chloride should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant.Dissolve 1 g sodium nitroprusside. in a 1000-mL volumetric flask which already contains about 800 mL water.Dissolve 25 g sodium hydroxide. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature.00 – 2. Make up to volume and check the pH and correct if necessary with HCl to 5. Let cool down and make up to volume. The dried ammonium chloride should be weighed as soon as it has reached the ambient temperature.2). 6. 7.Determinations. Na2[Fe(CN)5NO].2H2O. which already contains about 800 mL water. The solution is stable for one week. Let cool down and pipette 0 – 1. 6. The fine crystals should. PROCEDURE .Dissolve 2 g sodium dichloroisocyanurate. Remark : 1.2 .The absorbance (A) is plot versus mg/L nitrogen in the standard series. in a 1000-mL volumetric flask which already contains about 800 mL water.Pipette 33 mL concentrated sulphuric acid (96 %) in a volumetric flask. pH = 5. The solution is stable for one week. 8. Store in a dark coloured bottle. After the recommended heating procedure. nr 430AG-6) and mix.1 or 2.Dissolve 33 g potassium sodium tartrate. Add 24 g sodium citrate. in a 1000-mL volumetric flask.5 Sodium Dichloroisocyanurate . 6. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on. CALIBRATION AND STANDARDS 7.2H2O and dissolve. NaOH. C7H5NaO3 and make up to volume. C3N3O3Cl2Na. 7.4H2O.2 ± 0.2H2O. Just before drying. This is important.1 Standard Series . 6. any lumps should be cut down so that only fine crystals remain.

. April 1984.1 Krom.1 Measurement . A data management system and system controller are used.07139 * (a . Sodium Dichloroisocyanurate (6.Start the segmented-flow system according to the scheme given in figure 1. in g. 1980. In this way the measurements are checked continuously and the data output is in concentration units in the digests.L. expressed in mmol/kg N. REFERENCES 10. M. Spectrophotometric determination of ammonia.1 The nitrogen content in the dried plant material. in mg/L. CALCULATION 9. 9. Measure the absorbance of the standard series. in mg/L. Remark: 2. Determination of nitrogen fractions 8. The Analyst 109. w is the weight of plant material sample.2) Air Buffer Solution (6. b is the concentration of nitrogen in the blank digest.5) Sodium Nitroprusside (6.2) Sample Figure 1 Flow diagram for the determination of nitrogen by SFA. The Berthelot or indophenol reaction and its use in the analysis chemistry of nitrogen.b) * V / w in which: a is the concentration of nitrogen in the sample digest. The Analyst April 1980. 1984.2 Searle. a study of modified Berthelot reaction using salicylate and dichloroisocyanurate. the blanks and the sample digests at a wavelength of 660 nm.4) Sodium Salicylate (6. V is the total volume of digest at the end of the digestion procedure.3) Air Buffer Solution (6. in mL. P. is calculated by: 0.118 Determinations. 10. 10.

1 (extraction with water). D-naphtylamine and sulphanilamide are added. The colour reagent is known as the Griess-Ilosvay reagent.1 The reproducibility of determinations by this procedure should give. provided with ferrules for connection to the SFA tubing).2 Reduction column (a U-shaped glass tubing. Next.7 respectively 2. 2. reduction column. The nitrate is then reduced to nitrite by means of copper-coated cadmium.1 In a segmented-flow analysis (SFA) system. about 15 cm long and with internal diameter of 2 mm.C DETERMINATION OF NITRATE (+ NITRITE) BY SFA 1. INTERFERENCES 3. computer). a Skalar Segmented Flow Analyzer is used. 1. RANGE AND DETECTION LIMIT 2. 3. The dialysis serves to separate nitrate ions from interfering substances like colloids and coloured organic compounds.2 This determination may be carried out on extract 3. dialysis unit. but any SFA system will do.0 mmol/kg in the dried plant material). Nitrate ions from the extract pass the membrane and are taken in an understream of ammonium chloride. so that in the acid medium present a red-coloured diazo compound is formed.1 Segmented-flow analysis system (sampler. pump. Actually. at reasonable control and thorough sample preparation.Determinations. 5. APPARATUS 5.1 This procedure yields a standard curve that is linear up to approximately 65 mg/L N-NO3. NO3-unit. 2. photometer. In the authors' laboratory. PRINCIPLE OF THE METHOD 1. 3. PRECISION AND ACCURACY 4.14. Determination of nitrogen fractions 119 4. It may .2 The detection limit is approximately 0. Its absorbance is measured at a wavelength of 540 nm. 4.1 No interferences are expected.6 mg/L (0. the sum of NO3 and NO2 is determined here. Remarks: 1. The determination limit is approximately 0. 2. 5. Note. a coefficient of variation within 10 %. that with other systems the flow diagram may require adaptation.2 mg/L in the extract. the sample is first subjected to dialysis.

however. Make up to volume and mix well. in a 1000- mL volumetric flask which contains already about 800 mL water.3 Diluted Brij 35 .2 with ammonia solution. and 0. Note: it is advised to degas the reagent before adding the Brij 35. 6.00 – 2. Store in a dark coloured bottle. This SFA arrangement allows the determination of nitrite by simply shortcutting the reduction column. KNO3 (see remark 5).2 .120 Determinations. which already contains about 700 mL water.2 Buffer Solution pH = 8.Add 3 mL Brij 35 (30 %) (Sigma Chemical Co. NH4Cl. and dissolve. 6.Dissolve 39. any lumps should be cut down so that only fine crystals remain. Just before drying. C12H16Cl2N2. The dried potassium nitrate should be weighed as soon as it has reached the ambient temperature. Remark: 4.1 Stock Solution.2 Colour Reagent . Determination of nitrogen fractions be purchased filled with copper-coated cadmium from the SFA system manufacturer. nr 430 AG-6) and mix well. The fine crystals should. C6H8N2O2S.703 g potassium nitrate. carefully in a volumetric flask. CALIBRATION AND STANDARDS 7. H3PO4. After the recommended heating procedure. which already contains 800 ml water and make up to volume.00 mL of the stock solution (6. REAGENTS 6. Remark: 5. N-NO3 concentration 5500 mg/L . The potassium nitrate has to be dried at 105 °C for at least 2 hours just before weighing.00 – 3. This is important.5 g D-naphthyl ethylene diamine dihydrochloride.Dissolve 50 g of ammonium chloride. nr 430 AG-6) in a 1000-ml volumetric flask. the potassium nitrate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. . Add 3 mL of Brij 35 (30 %) (Sigma Chemical Co. 7. Adjust the pH to 8. which already contains about 800 mL water and make up to volume.Pipette 0 – 1. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. Make up to the mark with water. in a 1000-ml flask.1 Standard Series .1) into 100-mL volumetric flasks. NH4OH (25 %) and make up to volume. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on. This standard series has N-NO3 concentrations of 0 – 22 – 44 – 66 mg/L. 6. Hereafter add 10 g sulphanilamide. 6.Dilute the 150 mL o-phosphoric acid (85 %).

in g. V is the volume of water used for the extraction. Remark: 6. CALCULATION 9. in mg/L.2) (Re)sample Air Diluted Brij 35 (6. in mL. 9.Determinations. expressed in mmol/kg N-NO3. in mg/L.1 Measurement .1 The nitrate content in the dried plant material. . b is the concentration of nitrate in the blank extract.2) Air Buffer Solution (6. Colour Reagent (6. PROCEDURE 8. Measure the absorbance of the stardard series.The absorbance (A) is plot versus mg/L N-NO3 in the standard series.4) Sample Figure 1 Flow diagram for the determination of N-NO3 by SFA.4) Air Air Buffer Solution (6. 8. the blanks and the sample digests at a wavelength of 540 nm. A data management system and system controller are used. In this way the measurements are checked continuously and the data output is in concentration units in the digests.Start the segmented-flow system according to the scheme given in figure 1.b) * V / w in which: a is the concentration of nitrate in the sample extract.07139 * (a . Determination of nitrogen fractions 121 7.2 Calibration Curve . w is the weight of plant material sample. is calculated by: 0.

2.2 Magnetic stirrer. phosphate. These interferences are partly combated by lowering the pH to 4. bicarbonate.D DETERMINATION OF NITRATE-NITROGEN BY ISE 1. Remarks: 1. RANGE AND DETECTION LIMIT 2.. At lower levels the interferences by inorganic but especially organic anions are too strong.1 mmol/L in the extract. the nitrate ions are detected directly with an ion-selective electrode (ISE). . 5.1 After buffering the ionic strength of the water extracts by a phosphate solution. INTERFERENCES 3. 5. Thus the ionisation is decreased and the organic anions are partly complexed.1 The detection limit is approximately 0.1 Some anionic species interfere: chloride. oxalate. a coefficient of variation within 15 %. 3. 2.1 The reproducibility of determinations by this procedure should give.1 Potentiometer (pH/mV meter) with which a precision of better than 0.3 mmol/L (5 respectively 15 mmol/kg in the dried plant material).14.1 (extraction with water). at reasonable control and thorough sample preparation. Determination of nitrogen fractions 4. 1.0 and addition of cation exchange resin saturated with Al3+.122 Determinations. The determination limit is approximately 0. malate and malonate. APPARATUS 5.2 This determination may be carried out on extract 3. 5. the resin lowers the pH further to about 2.5-3. The addition of phosphate and Al-resin also serves the purpose of buffering the ionic strength. 1983). PRECISION AND ACCURACY 4. succinate. citrate.3 Indicator electrode: nitrate ion-selective electrode. PRINCIPLE OF THE METHOD 1.5 mmol/kg). fumarate. 4. This method may be used for the determination of nitrate in plant material only when the nitrate content is high (0. The nitrate concentration at which the interferences are negligible depends on the plant species (Novozamsky et al. acetate.5 mV can be obtained.

. in 100 mL water. AgNO3. After the recommended heating procedure. in some water and make up to 1 litre. Remark: 4. Remark: 5. The dried potassium nitrate should be weighed as soon as it has reached the ambient temperature. a wide standard series is necessary.Dissolve 242 g of aluminium chloride hexahydrate.Dissolve 0.Dissolve 2. AlCl3.4 Hydrochloric Acid Solution 4 mol/L . Al Concentration 0.0 – 20 mmol/L. 6.Add 330 mL of concentrated hydrochloric acid (36 %) to about 400 mL water and make up to 1 litre. however. any lumps should be cut down so that only fine crystals remain.Pipette 0. KNO3 (see remark 4) in some water in a 1000-mL volumetric flask and make up to volume.4 Reference electrode: Hg/Hg2SO4 electrode with saturated K2SO4 as contact electrolyte.6 Silver Solution . 20 . NO3 Concentration 20 mmol/L . 6. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature.form.00 mL of the stock solution (6. Just before drying.2 Buffer Solution. This is important.0220 g of potassium nitrate. the potassium nitrate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. in 2 litre water.00 – 3. 6.6H2O. Remark: 3. REAGENTS 6.30 – 1.0 . See also remark 7. CALIBRATION AND STANDARDS 7.06 – 0.2 g of potassium dihydrogen phosphate. The potassium nitrate has to be dried at 105 °C for at least 2 hours just before weighing.0 – 6. Since there are very large differences in nitrate levels in plant material. 6. in H+.10 – 0.50 mesh. KH2PO4. 7. This standard series has NO3 concentrations of 0.Determinations.00 – 10. a common calomel electrode can be used.1) into 100-mL volumetric flasks and make up to volume.00 – 30. 6.5 Aluminium Solution.1 Stock solution. The fine crystals should. Determination of nitrogen fractions 123 5. Dowex 50 W-X 8. pH 4.or Na+.50 mol/L .1 Standard Series .Dissolve 27.85 g of silver nitrate.3 Cation Exchange Resin.60 – 2. In practice.20 – 0. provided that the chloride leakage is very small and no Ag-resin is applied. Also the stock solution can be used as a standard solution. 6. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on.02 – 0.

this will remove the air bubble.00 mL of buffer solution (6.G.124 Determinations. Immerse both electrodes in the solution.5) until the pH of the percolate is equal to the pH of the influent (about pH 3). Remarks: 6. Rinse with water until the leachate is free from chloride. Add 5. 31: 239-248. then start stirring. It is recommended to use A3 size graph paper with a 3-decade logarithmic x-axis and a scale unit of 100 mm per decade. let the resin dry further on the air.5-min intervals until three subsequent readings have the same value. Pour the resin slurry on a Büchner funnel on which a filter paper is put. the blanks and the sample extracts into 50-mL beakers. Plot a calibration curve on semi-logarithmic paper and read the nitrate concentrations. If an air bubble sticks on the electrode membrane. then simply take the electrode out of the liquid and immerse it again. Neth.1 The nitrate content of the dried plant material.6). . Suck off the water until the resin looks dry. V is the volume of extractant used for the extraction of w gram sample. 10.. Houba. is calculated by: a*V/w in which: a is the nitrate concentration in the sample extracts. in mL.Agric.0. All measurements must be done at constant temperature. expressed in mmol/kg NO3. Determination of nitrogen fractions 8. 8.2 Measurements .00 mL of the standard series. 1983.4). CALCULATION 9.1 Novozamsky. REFERENCES 10. Leach dropwise with about 1 litre of 4 M hydrochloric acid (6.5 litre of aluminium solution (6. V.J.Sci. 9. I. check with silver solution (6. Rinse with water until neutral or weakly acid (pH about 5). in mmol/L.6 grams) of resin. 8. van Eck.3 .Pipette 5. Transfer the resin to the percolation tube with the help of water to prevent the formation of air bubbles. Read the potential (mV) while stirring. in g.J.3). Then leach the resin dropwise with approximately 1. Introduce a glass wool tuft down into a percolation tube. D.1 Preparation of resin . van der Eijk and R. 7. w is the weight of plant material sample.2) and a spoonful (0. take readings at 0.Weigh out 250 g of cation exchange resin (6. PROCEDURE 8. Place the beaker on a magnetic stirrer and put a small plastic-coated iron bar in the beaker. Notes on determinations of nitrate in plant material.

1 (extraction with water). but any SFA system will do. PRINCIPLE OF THE METHOD 1.1 Segmented-flow analysis system (sampler. 5.1 mg/L in the extract. the sample is first subjected to dialysis. 4. of which the absorbance is measured at a wavelength of 540 nm. Note that with other systems the flow diagram may require adaptation. NO2-unit.1 In a segmented-flow analysis (SFA) system. pump. 1. INTERFERENCES 3. 2. APPARATUS 5. Nitrite ions from the extract pass the membrane and are taken in an understream of ammonium chloride. a coefficient of variation within 10 mmol + 10%.3 respectively 1 mmol/kg in the dried plant material). 2. a Skalar Segmented Flow Analyzer is used.E DETERMINATION OF NITRITE BY SFA 1.1 The reproducibility of determinations by this procedure should give. The colour reagent is known as the Griess-Ilosvay reagent. In the authors' laboratory. at reasonable control and thorough sample preparation.2 This determination may be carried out on extract 3.Determinations. 2. PRECISION AND ACCURACY 4. Determination of nitrogen fractions 125 4. the nitrite forms a red-coloured diazo compound. The dialysis serves to separate ions from interfering substances like colloids and coloured organic compounds.1 This procedure yields a standard curve that is linear up to approximately 3 mg/L N- NO2. computer). 3.3 mg/L (0. By addition of D-naphtylamine and sulphanilamide in acid medium. Remarks: 1. dialysis unit.1 No interferences are expected.14. The determination limit is approximately 0. . RANGE AND DETECTION LIMIT 2.2 The detection limit is approximately 0.

In the authors' laboratory the SFA arrangement of determination 4.2 Standard Solution.2 with ammonia solution.1 Standard Series .1 Stock Solution. nr 430AG-06) and mix well. C12H16Cl2N2.5 g D-naphthyl ethylene diamine dihydrochloride. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. Note: it is advised to degas the reagent before adding the Brij 35. 6. 6. N-NO2 concentration 2000 mg/L .00 mL of the standard solution (6. NH4OH (25 %) and make up to volume. Store in a dark coloured bottle. Remark: 4.Add 3 mL Brij 35 (30 %) (Sigma Chemical Co. and 0. The fine crystals should. 7. any lumps should be cut down so that only fine crystals remain. NaNO2 (see remark 4). H3PO4.1) in a 100-mlL volumetric flask and make up to volume with water. pH = 8. 6. After the recommended heating procedure.6) and make up to volume. This is important. N-NO2 concentration 100 mg/L .Dilute the 150 mL o-phosphoric acid (85 %). which already contains 800 ml water and make up to volume. in a 1000-ml flask. The dried sodium nitrite should be weighed as soon as it has reached the ambient temperature.Dissolve 50 g of ammonium chloride. CALIBRATION AND STANDARDS 7. Adjust the pH to 8. carefully in a volumetric flask.Pipette into 100-mL volumetric flasks 0 – 1. NH4Cl. 7.852 g sodium nitrite.2 .C (nitrate + nitrite) is used by simply shortcutting the Cu-Cd reduction column.Dissolve 9. This standard series has NO2 concentrations of 0 – 10 – 20 – 30 mg/L.3 Colour Reagent .The absorbance (A) is plot versus mg/L N-NO2 in the standard series. in a 1000- mL volumetric flask which contains already about 800 mL water.00 – 3. 6. Hereafter add 10 g sulphanilamide. Just before drying. nr 430AG-06) in a volumetric flask which contains already contains about 800 mL water and make up to volume. The sodium nitrite has to be dried at 105 ° C for at least 2 hours just before weighing.126 Determinations. . and dissolve. the sodium nitrite should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant.4 Diluted Brij 35 . 6.Pipette 5 mL stock solution (6. Add 3 mL of Brij 35 (30 %) (Sigma Chemical Co.00 – 2. which already contains about 700 mL water. REAGENTS 6. C6H8N2O2S.3 Buffer Solution. Determination of nitrogen fractions Remark: 3.14. however. Make up to volume and mix well.2 Calibration Curve .

3) (Re)sample Air Diluted Brij 35 (6.Determinations.b) * V / w in which: a is the concentration of nitrite-nitrogen in the sample extract.1 Measurement . PROCEDURE 8.2 (6.1 The nitrite content in the dried plant material. expressed in mmol/kg N-NO2. 5) Air Air Buffer Solution pH=8. V is the total volume of water used for the extraction. b is the concentration of nitrite-nitrogen in the blank extract.3) Air Buffer Solution pH=8. in mg/L. In this way the measurements are checked continuously and the data output is in concentration units in the digests. Colour reagent (6. w is the weight of plant material sample. Remark: 5. is calculated by: 0. Measure the absorbance at a wavelength of 540 nm.4) Sample Figure 1. Flow diagram for the determination ot N-NO2 by SFA. in mg/L. place them in the automatic sampler and put the segmented-flow system into operation according to the scheme given in figure 1. in g.2 (6. 9. . CALCULATION 9. in mL. A data management system and system controller are used. Determination of nitrogen fractions 127 8.07139 * (a .Transfer blanks and sample extracts into polycarbonate test tubes.

PRINCIPLE OF THE METHOD 1. digest 2. digest 2. .7 (digestion by dry-ashing followed by treatment with HF).2 (digestion with H2SO4 . 4. INTERFERENCES 3.0-21 mmol/kg in the dried plant material).0 mg/L in the digest.Se). 1.128 Determinations.salicylic acid .salicylic acid .15. 3. The determination limit is approximately 3.1 To prevent ionisation interferences. 5. The sodium atoms thus formed emit radiation of which the intensity is measured at a wavelength of 589.4 (digestion with HNO3 - H2O2 .1 The sample is vaporised in an air-propane flame and the sodium compounds are atomised. APPARATUS 5.2 Since the sodium atomic emission line finds itself in the wavelength region of a calcium oxide emission band.1 Flame atomic emission spectrometer.1 This procedure yields a standard curve that is linear up to approximately 15 mg/L Na.HF).H2O2).0 mg/L (6.HF) and digest 2.0 nm. PRECISION AND ACCURACY 4. 3.2 This determination may be carried out on 2. a coefficient of variation within 10 %.3 (microwave digestion with HNO3 .A DETERMINATION OF SODIUM BY FLAME AES 1.15 DETERMINATION OF SODIUM 4.H2O2 .H2O2 . Determination of sodium 4. cesium is added to act as an ionisation buffer.1 The reproducibility of determinations by this procedure should give.1 digest (digestion with H2SO4 . too high results will be found if calcium is present in the digest. 2.2 The detection limit is approximately 1. at reasonable control and thorough sample preparation. RANGE AND DETECTION LIMIT 2. digest 2. Lanthanum is used as a releasing agent to release Ca from the interfering compounds. 2.

3.Dissolve 1. in a 1000-mL volumetric flask and make up to the mark with water.6H2O. Let cool down and make up to the mark with water. The cesium solution (6.00 – 6. The cesium chloride should be of the highest analytical grade (‘pro analysis’).00 – 12.7 (see Interferences 3.4) or 1. CsCl. because a lower quality (e.1A Stock Solution.2B Cesium-Lanthanum Solution. Just before drying. Remarks: 1.542 g sodium chloride.1A or 6. 6. Na concentration 1000 mg/L .The emission counts are plot versus mg/L sodium in the standard series. After the recommended heating procedure. 3.00 mL of the stock solution (6.2). in some water in a 1000-mL volumetric flask and make up to the mark with water. and 3. CsCl.1 g/L - Dissolve 1.7). not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on. 3.1 or 2. the sodium chloride should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. 7.5 mL concentrated sulphuric acid (96 %) (digestion 2. Add 4.1 g/L. Na concentration 1000 mg/L .1B Stock Solution. ‘reinst' = ‘most pure’) contains much more Na. whereas the cesium- lanthanum solution (6.2. . 7.g. NaCl (see remark 1).1 g/L .Determinations. any lumps should be cut down so that only fine crystals remain. 2.00 – 9. La concentration 1. 6. in a 1000-mL volumetric flask and make up to the mark with water.43 g lanthanum nitrate hexahydrate.2A Cesium Solution. 10 mL concentrated nitric acid (65 %) (digestion 2. This is important. however. Cs concentration 1.19507.2 Calibration Curve . Cs concentration 1. La(NO3)3. The sodium chloride has to be dried at 200 °C for at least 24 hours just before weighing. REAGENTS 6.1 and 2. 6.0 mL concentrated hydrochloric acid (36 %) (digestion 2.1 Standard Series . Determination of sodium 129 6.2A) should be used for digests 2. 2. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. The dried sodium chloride should be weighed as soon as it has reached the ambient temperature. CALIBRATION AND STANDARDS 7.4 g cesium chloride.Merck nr 1. The fine crystals should.2).00 – 15. This standard series has Na concentrations of 0 – 30 – 60 – 90 – 120 – 150 mg/L.4 g cesium chloride.Dissolve 2.3).4 and 2.0 mL concentrated nitric acid (65 %) (digestion 2.Pipette 0 – 3.2B) should be used for digests 2.1B) into 100-mL volumetric flasks which already contain 40 mL water.

a simple emission spectrometer ("flame photometer") may only be supplied with a so-called Na filter. b is the concentration of sodium in the blank digest.130 Determinations. Make sure that these are interference filters. since glass filters are not selective enough. Determination of sodium Remarks: 4. Measure in the diluted standard series. 7.1 The total sodium content in the dried plant material.3. in mg/L. The calibration curve should be nearly linear. CALCULATION 9. the blanks and the sample digests the Na concentration with flame AES at a wavelength of 598. using an air-propane flame. in g.Dilute the standard series.b) * V / w in which: a is the concentration of sodium in the sample digest. A mix standard series can be used for simultaneous measurements with Flame-AES (Ca.1 and 2.1 Measurement .7). Instead of indicating a wavelength. since the Cs concentration is high enough to counteract the greater tendency to ionisation.04350 * (a . expressed in mmol/kg Na.2) or with the cesium- lanthanum solution (6. PROCEDURE 8. in mg/L. Remarks: 6.2A) (digests 2. .4 and 2.0 nm. the blanks and the sample digests 1 + 9 (v/v) either with the cesium solution (6. in mL.2B) (digests 2. w is the weight of plant material sample. 5. K and Na). V is the total volume of digest at the end of the digestion procedure. 9. 8. An air-acetylene flame can be used also. 2. is calculated by: 0.

where all components are vaporised. Just before drying. Na concentration 1000 mg/L . 6.1 This procedure yields a standard curve that is linear up to at least 60 mg/L Na. 6.542 g sodium chloride. INTERFERENCES 3. Na concentration 1000 mg/L . digest 2. 4. NaCl (see remark 1).1B Stock Solution.005 mg/L in the digest.2 The detection limit is approximately 0. a coefficient of variation within 5 %. PRECISION AND ACCURACY 4.1A Stock Solution.592 nm. PRINCIPLE OF THE METHOD 1.1 The reproducibility of determinations by this procedure should give.1 digest (digestion with H2SO4 .HF). at reasonable control and thorough sample preparation.15.HF) and digest 2.salicylic acid . Sodium compounds are dissociated and excited.salicylic acid .Dissolve 2. 1. The determination limit is approximately 0.H2O2). 3.B DETERMINATION OF SODIUM BY ICP-OES 1. Remark: 1.015 mg/L (0. This is . APPARATUS 5.Determinations.3 (microwave digestion with HNO3 .612 nm). any lumps should be cut down so that only fine crystals remain. The sodium chloride has to be dried at 200 °C for at least 24 hours just before weighing.7 (digestion by dry-ashing followed by treatment with HF). digest 2. digest 2.1 Interferences are expected from Ba (589. Determination of sodium 131 4. 2. 2.Merck nr 1.22 mmol/kg in the dried plant material).1 Solutions with sodium compounds are nebulised into an argon plasma. and then emit radiation of which the intensity is measured at a wavelength of 589. REAGENTS 6.H2O2 .2 (digestion with H2SO4 .2 This determination may be carried out on 2.07 respectively 0.1 Inductively coupled plasma optical emission spectrometer.19507. in some water in a 1000-mL volumetric flask and make up to the mark with water.H2O2 .4 (digestion with HNO3 - H2O2 . RANGE AND DETECTION LIMIT 2.Se). 5.

b is the concentration of sodium in the blank digest. After the recommended heating procedure. A data management system and system controller are used. 4. Cr.The emission counts are plot versus mg/L sodium in the standard series. is used in the author's laboratory as an internal standard to compensate for matrix effects. Na.00 – 6. w is the weight of plant material sample.1 or 2. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. however.1 The total sodium content in the dried plant material. .04350 * (a . expressed in mmol/kg Na. Ni. 10 mL concentrated nitric acid (65 %) (digestion 2.5 mL concentrated sulphuric acid (96 %) (digestion 2. K. CALIBRATION AND STANDARDS 7.408 nm. P. Let cool down and make up to the mark with water.0 mL concentrated nitric acid (65 %) (digestion 2.132 Determinations. Co. 7.Pipette 0 – 1. Cu. PROCEDURE 8.592 nm.2).2 Calibration Curve . Add either 4.4) or 1. V is the total volume of digest at the end of the digestion procedure. in mL.00 – 2. 7. at an wavelength of431.Measure in the standard series. As a check all standards can be measured as samples.b) * V / w in which: a is the concentration of sodium in the sample digest. A mix standard series can be used for simultaneous measurements with ICP-OES (Al. Remark: 2. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series. is calculated by: 0. in mg/L. the blanks and the sample digests the Na concentration with the ICP-OES at a wavelength of 589. S and Zn).1 Standard Series . which already contain 40 mL water.00 mL of the stock solution (6. In this way the measurements are checked continuously and the data output is in concentration units in the digests.1 Measurement . Remarks: 3. 8. 9. in g. Determination of sodium important. Mg.0 mL concentrated hydrochloric acid (36 %) (digestion 2. 5. 3. Ca. Scandium (5 mg/L). At this wavelength a (fitted) background correction is used. Cd.1A or 6.7). The fine crystals should. The dried sodium chloride should be weighed as soon as it has reached the ambient temperature. Mn. This standard series has Na concentrations of 0 – 10 – 20 – 60 mg/L.1B) into 100-mL volumetric flasks. CALCULATION 9. in mg/L. the sodium chloride should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant.3). Fe.

a coefficient of variation within 5 % + 5 mg/kg.1 This procedure yields a standard curve that is linear up to approximately 2 mg/L Ni.A DETERMINATION OF NICKEL BY FLAME AAS 1. 4. Ni concentration 1000 mg/L . using background correction. PRECISION AND ACCURACY 4. nickel compounds are atomised and the nickel atoms thus formed absorb radiation from a hollow cathode lamp. The absorbance is measured at a wavelength of 232.1 mg/L in the digest. digest 2. at reasonable control and thorough sample preparation.HF). Ni concentration 1000 mg/L . in about 500 mL water in a 1000-mL volumetric flask and make up to volume. APPARATUS 5.1B Stock Solution.HF) and digest 2. 5. INTERFERENCES 3.1 The sample is nebulised into an air-acetylene flame.H2O2 .4 (digestion with HNO3 . 6.16 DETERMINATION OF NICKEL 4.6H2O. The determination limit is approximately 0. 1.16.19792. 2.953 g nickel nitrate hexahydrate. 2. RANGE AND DETECTION LIMIT 2.1A Stock Solution. Ni(NO3)2.3 mg/L (15-38 mg/kg in the dried plant material).Merck nr 1. 3.2 The detection limit is approximately 0.1 To avoid interferences as much as possible.2 This determination may be carried out on digest 2. Determination of nickel 133 4.7 (digestion by dry-ashing followed by treatment with HF). 6.1 Atomic absorption spectrophotometer with a device for correcting background absorption. . where it is vaporised.0 nm.Determinations. PRINCIPLE OF THE METHOD 1.H2O2 .3 (microwave digestion with HNO3 . REAGENTS 6.Dissolve 4.1 The reproducibility of determinations by this procedure should give. background correction is necessary.

134 Determinations; Determination of nickel

6.2 Standard Solution, Ni concentration 10 mg/L - Pipette 1.00 mL stock solution (6.1A
or 6.1B) into a 100-mL volumetric flask and make up to volume.

Remark:
1. Ni(NO3)2.6H2O may absorb water on standing. The reagent should be standardised by titration
with EDTA at pH 10 with murexide as an indicator.

7. CALIBRATION AND STANDARDS

7.1 Standard Series - Pipette 0 – 1.00 – 2.00 – 5.00 – 10.00 – 15.00 – 20.00 mL of the
standard solution (6.2) into 100-mL volumetric flasks, which already contain 40 mL
water. Add either 10 mL concentrated nitric acid (65 %) (digestion 2.3), 3.0 mL
concentrated nitric acid (65 %) (digestion 2.4) or 1.0 mL concentrated hydrochloric
acid (36 %) (digestion 2.7). Let cool down and make up to the mark with water.
This standard series has Ni concentrations of 0 – 0.1 – 0.2 – 0.5 – 1.0 – 1.5 – 2.0
mg/L.

7.2 Calibration Curve - The absorbance (A) is plot versus mg/L nickel in the standard
series.

8. PROCEDURE

8.1 Measurement – Measure in the standard series, the blanks and sample digests the
Ni concentration with flame AAS at a wavelength of 232.0 nm, using a just blue
(stoichiometric) air-acetylene flame. Use scale expansion if necessary.

9. CALCULATION

9.1 The total nickel content of the dried plant material, expressed in Pg/kg Ni, is
calculated by:
1000 * (a - b) * V / w
in which:
a is the concentration of nickel in the sample digest, in mg/L;
b is the concentration of nickel in the blank digest, in mg/L;
V is the total volume of digest at the end of the digestion procedure, in mL;
w is the weight of plant material sample, in g.

Determinations; Determination of nickel 135

4.16.B DETERMINATION OF NICKEL BY ICP-OES

1. PRINCIPLE OF THE METHOD

1.1 Solutions with nickel compounds are nebulised into an argon plasma, where all
components are vaporised. Nickel compounds are dissociated and excited, and
then emit radiation of which the intensity is measured at a wavelength of 231.604
nm.

1.2 This determination may be carried out on digest 2.3 (microwave digestion with
HNO3 - H2O2 - HF), digest 2.4 (digestion with HNO3 - H2O2 - HF), digest 2.6
(digestion with HNO3 - HClO4 - H2SO4) and digest 2.7 (digestion by dry-ashing
followed by treatment with HF).

2. RANGE AND DETECTION LIMIT

2.1 This procedure yields a standard curve that is linear up to at least 2 mg/L Ni.

2.2 The detection limit is approximately 0.006 mg/L in the digest. The determination
limit is approximately 0.018 mg/L (2 respectively 6 mg/kg in the dried plant
material).

3. INTERFERENCES

3.1 No interferences are expected.

4. PRECISION AND ACCURACY

4.1 The reproducibility of determinations by this procedure should give, at reasonable
control and thorough sample preparation, a coefficient of variation within 5 %.

5. APPARATUS

5.1 Inductively coupled plasma optical emission spectrometer.

6. REAGENTS

6.1A Stock Solution, Ni concentration 1000 mg/L - Merck nr 1.02640.

6.1B Stock Solution, Ni concentration 1000 mg/L - Dissolve 4.953 g nickel nitrate
hexahydrate, Ni(NO3)2.6H2O, in about 500 mL ultra pure water in a 1000-mL
volumetric flask and make up to volume.

6.2 Standard Solution, Ni concentration 100 mg/L - Pipette 1 mL concentrated nitric
acid (65 % s.p.) in a 100-mL polythene volumetric flask which already contains

136 Determinations; Determination of nickel

about 50 mL ultra pure water. Add 10.00 mL stock solution (6.1A or 6.1B) and
make up to volume with ultra pure water.

7. CALIBRATION AND STANDARDS

7.1 Standard Series - Pipette 0 – 1.00 – 2.00 mL of the stock solution (6.1A or 6.1B)
into 100-mL volumetric flasks, which already contain 40 mL water. Add either 10
mL concentrated nitric acid (65 %) (digestion 2.3), 3.0 mL concentrated nitric acid
(65 %) (digestion 2.4) or 1.0 mL concentrated hydrochloric acid (36 %) (digestion
2.7). Let cool down and make up to the mark with water. This standard series has
Ni concentrations of 0 – 1 – 2 mg/L.

7.2 Calibration Curve - The emission counts are plot versus mg/L nickel in the
standard series.

Remark:
1. A mix standard series can be used for simultaneous measurements with ICP-OES (Al, Ca,
Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, S and Zn).

8. PROCEDURE

8.1 Measurement - Measure in the standard series, the blanks and the sample digests
the Ni concentration with the ICP-OES at a wavelength of 231.604 nm. At this
wavelength a (left and right side) background correction is used.

Remarks:
2. A data management system and system controller are used. In this way
the measurements are checked continuously and the data output is in
concentration units in the digests.
3. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES
only with the highest and zero standard of the standard series. As a check
all standards can be measured as samples.
4. Scandium (5 mg/L), at an wavelength of 255.235 nm, is used in the
author's laboratory as an internal standard to compensate for matrix
effects.

9. CALCULATION

9.1 The total nickel content in the dried plant material, expressed in mg/kg Ni, is
calculated by:
(a - b) * V / w
in which:
a is the concentration of nickel in the sample digest, in mg/L;
b is the concentration of nickel in the blank digest, in mg/L;
V is the total volume of digest at the end of the digestion procedure, in mL;
w is the weight of plant material sample, in g.

a coefficient of variation within 10 %.Dissolve 4.1 The 44Ca16O molecule has the same mass as 60Ni. 1. digest 2. 3. and quantified with a channel electron multiplier.1A Stock Solution.2 This determination may be carried out on digest 2.Merck nr 1. . RANGE AND DETECTION LIMIT 2. 2. A correction factor can be applied.1 Solutions with nickel compounds are nebulised into an argon plasma. Ni concentration 1000 mg/L . at reasonable control and thorough sample preparation.7 (digestion by dry-ashing followed by treatment with HF).1 This procedure yields a standard curve that is linear up to at least 50 Pg/L Ni. A correction factor can be applied. where all components are vaporised.3 (microwave digestion with HNO3 .2 The detection limit is approximately 0. sorted according to their mass-to-charge ratios. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer. Determination of nickel 137 4.H2O2 .C DETERMINATION OF NICKEL BY ICP-MS 1.4 (digestion with HNO3 .1B Stock Solution. 2. PRINCIPLE OF THE METHOD 1. 4.953 g nickel nitrate hexahydrate. The determination limit is approximately 0.1 The reproducibility of determinations by this procedure should give.HF) and digest 2. APPARATUS 5. in about 500 mL ultra pure water in a 1000-mL volumetric flask and make up to volume.HF). 5.H2O2 . INTERFERENCES 3. Ni(NO3)2. 6.02 µg/L in the digest. Nickel is determined at mass 60 or 62 amu. PRECISION AND ACCURACY 4.1 Inductively coupled plasma mass spectrometer. 6.6H2O.16.06 µg/L (7 respectively 21 µg/kg in the dried plant material).Determinations. REAGENTS 6. The 46Ti16O molecule has the same mass as 62Ni. Ni concentration 1000 mg/L .02640.

Remarks: 3.00 mL stock solution (6. 7. As. . Add either 1. b is the concentration of nickel in the blank digest.3 mL concentrated nitric acid (65 %) (digestion 2. V is the total volume of digest at the end of the digestion procedure. w is the weight of plant material sample. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series. Ni. Mn.2 Standard Solution. 9. Add 1. As a check all standards can be measured as samples.1 mL concentrated hydrochloric acid (36 %) (digestion 2.) in a 1000-mL polythene volumetric flask which already contains about 500 mL ultra pure water.00 mL of the standard solution (6. Let cool down and make up to the mark with ultra pure water. A data management system and system controller are used. in g. in mL. Use a correction factor if necessary.138 Determinations. Ni(NO3)2.2) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks. CALCULATION 9.1 Measurement – Measure in the standard series.Pipette 0 – 1. Determination of nickel 6. V and Zn).2 Calibration Curve . Cr. 7.b) * V / w in which: a is the concentration of nickel in the sample digest.p. Co. This standard series has Ni concentrations of 0 –10 – 20 – 50 µg/L. the blank digests and sample digests the Ni concentration with the ICP-MS at a mass of 60 or 62 amu. Ni concentration 1 mg/L . Sn. The reagent should be standardised by titration with EDTA at pH=10 with Murexide as an indicator. Sb. In this way the measurements are checked continuously and the data output is in concentration units in the digests.00 – 2. PROCEDURE 8. in Pg/L. Remark: 2. 8. Cu.4) or 0. in Pg/L. is calculated by: (a .1B) and make up to volume with ultra pure water.0 mL concentrated nitric acid (65 %) (digestion 2. 4.3). Cd. Pb. Remark: 1. A mix standard series can be used for simultaneous measurements with ICP-MS (Al. CALIBRATION AND STANDARDS 7.1A or 6.1 The total nickel content in the dried plants material.The counts per second are plot versus Pg/L nickel in the standard series.Pipette 1 mL concentrated nitric acid (65 % s. expressed in µg/kg Ni.7).1 Standard Series . 0.6H2O may absorb water on standing.00 – 5.

2.1 Spectrophotometer equipped with a flow through cell.2 The detection limit is approximately 0.1 This procedure yields a standard curve that is linear up to approximately 5 mg/L PO4.Determinations. RANGE AND DETECTION LIMIT 2. The blue colour varies with the redox conditions of the medium and with pH. a coefficient of variation within 5 % + 5 mmol/kg.2 (digestion with H2SO4 .2 This determination may be carried out on digest 2. 5.Se) and digest 2.1 Arsenic and Silica .17 DETERMINATION OF PHOSPHORUS 4. INTERFERENCES 3. PRECISION AND ACCURACY 4.1 (digestion with H2SO4 .A DETERMINATION OF TOTAL PHOSPHORUS BY SPECTROPHOTOMETRY 1. PRINCIPLE OF THE METHOD 1. At a wavelength of 880 nm a very sensitive and stable measurement of P is possible. orthophosphates form a yellow-coloured complex with molybdate ions. The determination limit is approximately 0. Sb and Mo leads after reduction with ascorbic acid to the formation of a very stable blue-coloured phosphormolybdenum complex. 2.salicylic acid .03 mg/L in the digest.1 In an acidic medium.As5+ and Si4+ form similarly coloured complexes under these conditions. Determination of phosphorus 139 4.17. Remark: 1.5 mmol/kg in the dried plant material).1 The reproducibility of determinations by this procedure should give. 3.2 respectively 0. at reasonable control and thorough sample preparation. Both interferences are negligible at the low concentrations. 4.1 mg/L (0. . The combination of P.H2O2 .salicylic acid . which are normally present in these plant material digests. 1. APPARATUS 5.H2O2).

in about 900 mL water in a volumetric flask of 1000 mL. any lumps should be cut down so that only fine crystals remain.1B Stock Solution. C6H8O6.5 Sulphuric Acid Solution 2.6) with 300 mL ultra pure water.H2O2).Dissolve 0. Merck nr 13908.274 g potassium antimonyl tartrate. 5. in ultra pure water and make up to 100 mL with ultra pure water.Wetting agent Aerosol 22. Remarks: 2.1 (digestion with H2SO4 .Dissolve 1.5 mol/L .2 Ascorbic Acid Solution .Merck nr 1.salicylic acid . 6. 30 mL ascorbic acid solution (6.19898.H2O2 - Se) are to be measured. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on.Dilute carefully.4H2O. since demineralised water may contain varying amounts of Si. however.Add successively with a graduated cylinder and mix after each addition: 50 mL sulphuric acid (6.3 Ammonium Molybdate Solution .3). After the recommended heating procedure.1A Stock Solution.5 mL of anti-coagulating agent (6. The potassium dihydrogen phosphate has to be dried at 105 °C for at least 2 hours just before weighing. (NH4)6Mo7O24.5). KH2PO4 (see remark 2). in portions.432 g potassium dihydrogen phosphate.6 Anti-coagulation Agent .Mix 80 mL of the mixed reagent (6. Determination of phosphorus 6.2 (digestion with H2SO4 . For this determination. The fine crystals should. Prepare fresh daily. where no Se is used. Allow the mixture to cool off and make up to volume with ultra pure water. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. if samples of digestion 2.7 Mixed Reagent . Make up to 1000 mL with water.6). all solutions must be prepared with ultra pure water. 3. PO4 concentration 1000 mg/L . 6.salicylic acid .4 Potassium Antimonyl Tartrate Solution . REAGENTS 6. 6. the potassium dihydrogen phosphate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. 6. KSbOC4H4O6.Dissolve 40 g ammonium molybdate tetrahydrate.8 Diluted Mixed Reagent . This solution should be stored in a bottle made of hard glass. For digest 2.Dissolve 1. in 100 mL ultra pure water and mix.76 g ascorbic acid.140 Determinations. add 0.5H2O. the anti- coagulating agent is better left out because it slows down the colour formation . 15 mL ammonium molybdate solution (6. 140 mL concentrated sulphuric acid (96 %) in about 500 mL ultra pure water in a 1000-mL volumetric flask. 6. 4. This solution should be stored in a bottle made of hard glass. 6. PO4 concentration 1000 mg/L . Prepare fresh daily. The dried potassium dihydrogen phosphate should be weighed as soon as it has reached the ambient temperature.4). 6. Just before drying.2) and 5 mL potassium antimonyl tartrate solution (6. 6. This is important. in ultra pure water and make up to 1000 mL.

00 – 5.Determinations. Measure the absorbance in a 1-cm cuvette at a wavelength of 880 nm. This standard series has PO4 concentrations of 0 – 10 – 20 – 30 – 40 – 50 mg/L.1B) into 100-mL volumetric flasks. 7.The absorbance (A) is plot versus mg/L phosphate in the standard series. 9.8) and mix. Only part of the Mo will be reduced. in mg/L.2 Calibration Curve .0 mL of the diluted standard series. in mg/L.1). Add 3. is calculated by: 0.00 – 2.8 mL of the diluted mixed reagent (6. CALCULATION 9. CALIBRATION AND STANDARDS 7.2).Pipette 0 – 1.5 mL concentrated sulphuric acid (96 %) (digestion 2.00 – 4. Add 4.Dilute the standard series.00 – 3. The phosphomolybdenum blue complex reaches its maximum intensity after 1 hour and is stable for at least 10 hours.1 The total phosphorus content in the dried plant material. the blanks and all digests 1+9 (v/v) with ultra pure water.b) * V / w in which: a is the concentration of phosphorus in the diluted sample digest.1 Measurement . Hence. V is the total volume of digest at the end of the digestion procedure. Determination of phosphorus 141 7. the diluted blanks and the diluted sample digests into test tubes.00 mL of the stock solution (6. in mL. 6+ 7.01053 * (a . in g. samples that have high phosphate concentrations cannot be diluted once that the blue colour has been formed. 8.1 or 2. expressed in mmol/kg P. Remarks: 6.2) or 1 hour (digest 2. Allow to stand for 10 min (digest 2. which already contain 40 mL ultra pure water. w is the weight of plant material sample. Pipette 1. b is the concentration of phosphorus in the diluted blank digest. Let cool down and make up to the mark with ultra pure water.1 Standard Series . . PROCEDURE 8.1A or 6.

PRINCIPLE OF THE METHOD 1.salicylic acid . PO4-unit. APPARATUS 5.1 Orthophosphates form a yellow-coloured complex with molybdate ions in an acid medium.1 Segmented-flow analysis system (sampler. computer). Note that with other systems the flow diagram may require adaptation.142 Determinations.8 mmol/kg in the dried plant material). a Skalar Segmented Flow Analyzer is used. 2.2 The detection limit is approximately 0. After addition of ascorbic acid and Sb. a blue-coloured phosphomolybdenum complex is formed.H2O2 . 3. which are normally present in these plant material digests. but any SFA system will do. INTERFERENCES 3.salicylic acid .1 The reproducibility of determinations by this procedure should give.17. 1.H2O2).2 This determination may be carried out on digest 2. 2. of which the absorbance is measured at a wavelength of 660 nm.Se) and digest 2. The determination is carried out as a so-called segmented-flow analysis (SFA). pump. Both interferences are negligible at the low concentrations. Remark: 1.2 (digestion with H2SO4 . . In the authors' laboratory. PRECISION AND ACCURACY 4. Sb is added to complete the reduction of the yellow phosphomolybdenum complex to the blue phosphomolybdenum complex.1 This procedure yields a standard curve that is linear up to approximately 60 mg/L P.1 As5+ and Si4+ form similarly coloured complexes under these conditions. The determination limit is approximately 0. 4. a coefficient of variation within 5 % + 5 mmol/kg. Determination of phosphorus 4.1 (digestion with H2SO4 . photometer. 5.B DETERMINATION OF TOTAL PHOSPHORUS BY SFA 1.15 mg/L (0.05 mg/L in the digest. at reasonable control and thorough sample preparation. RANGE AND DETECTION LIMIT 2.

Pipette 33 mL concentrated sulphuric acid (96 %) in a 1000-mL volumetric flask. 6. the potassium dihydrogen phosphate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. sodium dodecyl diphenyloxide disulphonate (45-47%).394 g potassium dihydrogen o-phosphate. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on.300 g potassium antimony tartrate. The fine crystals should.1 Stock Solution.7 Rinsing Liquid Sampler . After the recommended heating procedure.and mix.Dissolve 0. This solution is stable for one month at 4 oC. REAGENTS 6. which already contains about 800 mL ultra pure water. 3. Make up to volume.8 Sulphuric Acid Solution . . This is important. The dried potassium dihydrogen phosphate should be weighed as soon as it has reached the ambient temperature. Hereafter add 4.5 Diluted FFD6 .7 Ascorbic Acid . 6. and dissolve.4H2O.Determinations. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. P concentration 1000 mg/L .Dissolve 4. KH2PO4 (see remark 2) in a 1000-mL volumetric flask which already contains about 800 ultra pure water and make up to volume. in a 1000-mL volumetric flask which already contains about 800 mL ultra pure water and make up to volume. C6H8O6. 6.5H2O. 6. Allow cooling and make up to volume. sodium dodecyl diphenyloxide disulphonate (45-47%). 6.Pipette 2 mL FFD6. 6. (NH4)6Mo7O24.0. Just before drying. The potassium dihydrogen phosphate has to be dried at 105 °C for at least 2 hours just before weighing.Pipette 40 mL concentrated sulphuric acid (96 %) in a 1000-mL volumetric flask which contains already about 800 mL ultra pure water and let cool down.8 g ammonium molybdate.2 Potassium Antimony Tartrate Solution . however. any lumps should be cut down so that only fine crystals remain. This solution is stable for one week at 4 oC. sodium dodecyl diphenyloxide disulphonate (45-47%). add 2 mL FFD6. in a 100-mL volumetric flask which already contains about 80 mL ultra pure water and make up to volume. and mix well (see remark 3). Let cool down and make up to volume then add 2 mL FFD6. The ammonium molybdate chemicals must not be in contact with metal components. which contains already about 800 mL ultra pure water. Remark: 2. Add 20 mL stock solution potassium antimony tartrate (6.Dissolve 18 g ascorbic acid. Determination of phosphorus 143 6. in a 1000-mL volumetric flask which already contains about 800 mL ultra pure water.2) and make up to volume. K(SbO)C4H4H6.Pipette 40 mL concentrated sulphuric acid (96 %) in a 1000-mL volumetric flask.6 Ammonium Molybdate .

Measure the absorbance of the standard series. in g. CALIBRATION AND STANDARDS 7.Start the segmented-flow system according to the scheme given in figure 1. that contain already about 50 mL water.b) * V / w in which: a is the concentration of phosphorus in the sample digest. 4. 5.1) and dilute to volume. w is the weight of plant material sample.Pipette into 100-mL volumetric flasks.The absorbance (A) is plot versus mg/L phosphorus in the standard series. b is the concentration of phosphorus in the blank digest.00 – 4. is calculated by: 0. A data management system and system controller are used.1 Standard Series .2 Calibration Curve . V is the total volume of digest at the end of the digestion procedure. in mg/L.144 Determinations. Determination of phosphorus 7. Allow to cool. .00 mL of the stock solution (6. Measurements may. 7. the blanks and the sample digests at a wavelength of 660 nm. Then add 0 – 2.03229 * (a .1 Measurement . The absorbance is measured at 660 nm because the system is provided with a filter of that wavelength. 8.00 – 6. CALCULATION 9. 9.5 mL of concentrated sulphuric acid (96 %). The standard series has P concentrations of 0 – 20 – 40 – 60 mg/L. in mg/L. however. be taken at 720 nm or 880 nm as well.1 The total phosphorus content in the dried plant material. Remarks: 4. In this way the measurements are checked continuously and the data output is in concentration units in the digests. expressed in mmol/kg P. PROCEDURE 8. in mL.

6) Air Diluted FFD6 (6. Determination of phosphorus 145 Ascorbic Acid (6. .5) Air Sulphuric Acid Solution (6.4) Sample Figure 1 Flow diagram for the determination of phosphorus by SFA.3) Ammonium Molybdate (6.Determinations.

2. in about 900 mL water in a volumetric flask of 1000 mL. digest 2. PRINCIPLE OF THE METHOD 1. 6. REAGENTS 6.H2O2 . Make up to 1000 mL with water.HF). and then emit radiation of which the intensity is measured at a wavelength of 178. The determination limit is approximately 0. at reasonable control and thorough sample preparation. 6.Dissolve 2.7 (digestion by dry-ashing followed by treatment with HF).1 No interferences are expected.salicylic acid .1B Stock Solution. 1. 4.1 Solutions with phosphorus compounds are nebulised into an argon plasma. Determination of phosphorus 4.1A Stock Solution. INTERFERENCES 3.1 This procedure yields a standard curve that is linear up to at least 100 mg/L P. RANGE AND DETECTION LIMIT 2. PO4 concentration 2000 mg/L . digest 2.864 g potassium dihydrogen phosphate. KH2PO4 (see remark 1). APPARATUS 5.3 (microwave digestion with HNO3 .1 (digestion with H2SO4 .4 (digestion with HNO3 - H2O2 .Se) and digest 2. a coefficient of variation within 5 % + 5 mmol/kg. 5.1 Inductively coupled plasma optical emission spectrometer.04 mg/L in the digest.2 (digestion with H2SO4 .1 The reproducibility of determinations by this procedure should give.C DETERMINATION OF TOTAL PHOSPHORUS BY ICP-OES 1.salicylic acid .2 This determination may be carried out on digest 2. PRECISION AND ACCURACY 4.H2O2). Phosphorus compounds are dissociated and excited. P concentration 2000 mg/L – LPS Benelux nr 11289. 2.17.HF) and digest 2.222 nm.12 mg/L (0.2 mmol/kg in the dried plant material). where all components are vaporised.H2O2 .4 respectively 1.146 Determinations.2 The detection limit is approximately 0. 3. .

0 mL concentrated hydrochloric acid (36 %) (digestion 2. the potassium dihydrogen phosphate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. S and Zn). This standard series has PO4 concentrations of 0 – 10 – 20 – 100 mg/L. Mg. Remark: 2. CALIBRATION AND STANDARDS 7.Pipette 0 – 1. P.3). Determination of phosphorus 147 Remark: 1. any lumps should be cut down so that only fine crystals remain. 5. This is important. 9. Add either 10 mL concentrated nitric acid (65 %) (digestion 2.1A or 6. PROCEDURE 8. Scandium (5 mg/L). in mg/L. Ca.1B) into 100-mL volumetric flasks which already contain 40 mL water. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on. 3. is used in the author's laboratory as an internal standard to compensate for matrix effects. Cr. Na. The fine crystals should. Ni. The potassium dihydrogen phosphate has to be dried at 105 ºC for at least 2 hours just before weighing.1 The total phosphorus content in the dried plant material. K. Remarks: 3. Fe.00 – 2. Mn. Cu. 7. Cd. Just before drying.The emission counts are plot versus mg/L phosphorus in the standard series. A data management system and system controller are used. 4. the blanks and the sample digests the P concentration with the ICP-OES at a wavelength of 178. 8.b) * V / w in which: a is the concentration of phosphorus in the sample digest. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. A mix standard series can be used for simultaneous measurements with ICP-OES (Al. Let cool down and make up to the mark with water.0 mL concentrated nitric acid (65 %) (digestion 2.4) or 1.7). at a wavelength of 255. The dried potassium dihydrogen phosphate should be weighed as soon as it has reached the ambient temperature.03229 * (a . As a check all standards can be measured as samples. In this way the measurements are checked continuously and the data output is in concentration units in the digests. .00 mL of the stock solution (6. Co. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series. CALCULATION 9.1 Standard Series .2 Calibration Curve . At this wavelength a (fitted) background correction is used.222 nm. 7. expressed in mmol/kg P. is calculated by: 0. however.Measure in the standard series.1 Measurement . After the recommended heating procedure.Determinations.235 nm.00 – 10.

148 Determinations. Determination of phosphorus b is the concentration of phosphorus in the blank digest. in g. V is the total volume of digest at the end of the digestion procedure. w is the weight of plant material sample. in mg/L. . in mL.

The determination limit is approximately 0.Merck nr 1.1 The sample is nebulised into an air-acetylene flame. lead compounds are atomised and the lead atoms thus formed absorb radiation from a hollow cathode lamp.5-19 mg/kg in the dried plant material). 5. Pb concentration 1000 mg/L .Dissolve 1. 6.H2SO4) and digest 2. 4.18 DETERMINATION OF LEAD 4.4 (digestion with HNO3 .1 Flame atomic absorption spectrophotometer with a device for correcting background absorption. PRECISION AND ACCURACY 4. RANGE AND DETECTION LIMIT 2. digest 2.H2O2 .19776. at reasonable control and thorough sample preparation. Pb concentration 1000 mg/L .1B Stock Solution.HClO4 . APPARATUS 5.1A Stock Solution. 6.2 This determination may be carried out on digest 2. background correction is necessary. 2. Determination of lead 149 4.HF). 3. in some water in a 1000-mL volumetric flask and make up to volume. where it is vaporised.5985 g lead nitrate. 2. a coefficient of variation within 10 % + 10 mg/kg. PRINCIPLE OF THE METHOD 1. Pb(NO3)2.A DETERMINATION OF LEAD BY FLAME AAS 1.Determinations. The absorbance is measured at a wavelength of 217. .15 mg/L (7.6 (digestion with HNO3 .18. 1.H2O2 .3 (microwave digestion with HNO3 .2 The detection limit is approximately 0.1 To avoid interferences as much as possible.05 mg/L in the digest. digest 2.0 nm.7 (digestion by dry-ashing followed by treatment with HF). INTERFERENCES 3. using deuterium background correction.1 The reproducibility of determinations by this procedure should give.HF). REAGENTS 6.1 This procedure yields a standard curve that is linear up to approximately 2 mg/L Pb.

0 – 3.4). J.2 Standard Solution..J. 1987). Novozamsky. in mL. 7. in g.0 mg/L. E. b is the concentration of lead in the blank digest. Remark: 2.1B) into a 100-mL volumetric flask and make up to volume. REFERENCES 10. 0. CALIBRATION AND STANDARDS 7.0 nm.7).2) into 100-mL volumetric flasks.J.0 – 4. 8.5 – 1.1 Measurement . which already contain 40 mL. PROCEDURE 8. 41: 388-390.00 – 4. Determination of lead 6. In this case Smith-Hieftje or Zeeman backgroun correction should be used.J. Temminghoff.M.The absorbance (A) is plot versus mg/L lead in the standard series. 9.3). Use scale expansion if necessary. is calculated by: 1000 * (a .00 mL stock solution (6.150 Determinations.Pipette 0 – 0. 7. 10. V.0 mL concentrated nitric acid (65 %) (digestion 2.00 – 3. at a wavelength of 217. the blanks and the sample digests the Pb concentration with flame AAS.G.b) * V / w in which: a is the concentration of lead in the sample digest.0 mL concentrated hydrochloric acid (36 %) (digestion 2. Samples with high iron content may give too low results when applying a deuterium background correction system (Van der Lee et al. This standard series has Pb concentrations of 0 – 0.. Pb(NO3)2 may absorb water on standing. CALCULATION 9.1 The total lead content in the dried plant material.50 – 1. 1987.6) or 1.00 – 2. Let cool down and make up to the mark with water.0 – 2.1 Standard Series . w is the weight of plant material sample.1A or 6. The reagent should be standardised by titration with EDTA at pH 10 in the presence of tartrate ions with Eriochrome Black T as an indicator.45 concentrated sulphuric acid (96 %) (digestion 2.Pipette 10. Add either 10 mL concentrated nitric acid (65 %) (digestion 2. Background corrections in the determination of Cd and Pb by flame AAS in plant and soil samples with high Fe levels. water. 3. expressed in Pg/kg Pb. Pb concentration 100 mg/L . Remark: 1. in mg/L. Houba and I.Measure in the standard series.2 Calibration Curve . . Spectrosc. in mg/L.00 mL of the standard solution (6. V is the total volume of digest at the end of the digestion procedure. Appl.1 Van der Lee.

Pb concentration 40 mg/L . 2.H2O2 . 1. RANGE AND DETECTION LIMIT 2.1 Inductively coupled plasma optical emission spectrometer. PRINCIPLE OF THE METHOD 1.B DETERMINATION OF LEAD BY ICP-OES 1. and then emit radiation of which the intensity is measured at a wavelength of 220.1 This procedure yields a standard curve that is linear up to at least 2 mg/L Pb. 3.1A Stock Solution. 6.19776.4 (digestion with HNO3 . 5. at reasonable control and thorough sample preparation. INTERFERENCES 3.HF). Pb concentration 1000 mg/L .2 This determination may be carried out on digest 2.18. Pb concentration 1000 mg/L .1A or 6.1 Solutions with lead compounds are nebulised into an argon plasma. Determination of lead 151 4.00 mL stock solution (6. 4. APPARATUS 5.2 The detection limit is approximately 0. 2.1 No interferences are expected. REAGENTS 6.5985 g lead nitrate.HF) and digest 2.12 mg/L (13 respectively 40 mg/kg in the dried plant material). Pb(NO3)2.353 nm.04 mg/L in the digest.Determinations.2 Standard Solution. Lead compounds are dissociated and excited.7 (digestion by dry-ashing followed by treatment with HF). where all components are vaporised.1B) in a 100-mL volumetric flask and make up to volume with water. 6. The determination limit is approximately 0. Remark: . digest 2.1B Stock Solution.Merck nr 1. a coefficient of variation within 10 % + 10 mg/kg.Dissolve 1. in some water in a 1000-mL volumetric flask and make up to volume. 6.3 (microwave digestion with HNO3 .1 The reproducibility of determinations by this procedure should give. PRECISION AND ACCURACY 4.Pipette 4.H2O2 .

As a check all standards can be measured as samples. b is the concentration of lead in the blank digest. PROCEDURE 8.Pipette 0 – 1. 3.1 Measurement . K.0 mL concentrated nitric acid (65 %) (digestion 2.4) or 1. expressed in mg/kg Pb. This standard series has Pb concentrations of 0 – 1. V is the total volume of digest at the end of the digestion procedure. in g. Scandium (5 mg/L). since Pb and S (SO4) can not be used in one mix standard due to PbSO4 precipitation.7). is used in the author's laboratory as an internal standard to compensate for matrix effects. the blanks and the sample digests the Pb concentration with the ICP-OES at a wavelength of 220.1 The total lead content in the dried plant material. Determination of lead 1. The reagent should be standardised by titration with EDTA at pH 10 in the presence of tartrate ions with Eriochrome Black T as an indicator. Na.353 nm. At this wavelength a (left and right side) background correction is used. Remark: 2. . Add either 10 mL concentrated nitric acid (65 %) (digestion 2. CALCULATION 9. P. at a wavelength of 255. in mg/L.152 Determinations.Measure in the standard series. 5. In this way the measurements are checked continuously and the data output is in concentration units in the extracts. For simultaneous measurements with ICP-OES a mix standard series has to be used without Pb (Al.2) into 100-mL volumetric flasks which already contain 40 mL water. 9.The emission counts are plot versus mg/L lead in the standard series. A data management system and system controller are used. Pb(NO3)2 may absorb water on standing. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series.3). Mn. in mL. Mg.0 mL concentrated hydrochloric acid (36 %) (digestion 2.235 nm. Ca. w is the weight of plant material sample. CALIBRATION AND STANDARDS 7.0 – 2.b) * V / w in which: a is the concentration of lead in the sample digest. Cu. 7. in mg/L.0 mg/L. Remarks: 3. Fe. 7. Let cool down and make up to the mark with water.1 Standard Series .2 Calibration Curve . Cd. 8. 4. is calculated by: (a .00 – 2. S and Zn).00 mL of the standard solution (6.

4 (digestion with HNO3 .0 nm line (more sensitive) can be used.18.1 The reproducibility of determinations by this procedure should give.C DETERMINATION OF LEAD BY ETA-AAS 1. REAGENTS 6. INTERFERENCES 3.19776. at reasonable control and thorough sample preparation.8 µg/L in the digest. 5. PRINCIPLE OF THE METHOD 1.H2O2 .2 This determination may be carried out on digest 2. 1. 6. RANGE AND DETECTION LIMIT 2.1 To avoid interferences as much as possible. Pb concentration 1000 mg/L .3 nm.1 Electrothermal atomisation (graphite furnace) atomic absorption spectrometer with a device for correcting background absorption. However. Determination of lead 153 4.Determinations.7 (digestion by dry-ashing followed by treatment with HF).1 This procedure yields a standard curve that is linear up to approximately 50 µg/L Pb. a coefficient of variation within 10 %.3 (microwave digestion with HNO3 . 3. APPARATUS 5.4 µg/L (400-1000 Pg/kg in the dried plant material).HF). .H2O2 . 5.Merck nr 1. PRECISION AND ACCURACY 4. 2. The absorbance is measured at a wavelength of 283.1 Lead ions in the digest are subsequently dried. non-specific absorption is than more important and background correction has to be used. digest 2. Remark: 1. Alternatively the 217.2 The detection limit is approximately 2. The determination limit is approximately 8. ashed and vaporised by electrical heating in a graphite furnace. 2. The lead atoms thus formed absorb radiation from a hollow cathode lamp.2 Polythene cups. 4.1A Stock Solution.HF) and digest 2. background correction is necessary.

5985 g lead nitrate.7 Propanol-2 Solution 5 % .1 Standard Series . This standard series has Pb concentrations of 0 – 10 – 20 – 30 – 40 – 50 µg/L. 6. 6. Let cool down and dilute to volume.4 Matrix modifier.Pipette 1. 7.Pipette 1 mL concentrated nitric acid (65 % s. Add either 10 mL concentrated nitric acid (65 %) (digestion 2.7).2 % . Add 1.Dissolve 0. in some ultra pure water in a 1000-mL volumetric flask and make up to volume.The absorbance (A) is plot versus mg/L lead in the standard series.154 Determinations.1B Stock Solution.1 Measurement . Pb(NO3)2. Palladium(II)chloride 0.Pipette 0 – 1.1B) and make up to volume with ultra pure water.) in a 1000-mL polythene volumetric flask which already contains about 500 mL ultra pure water.00 – 2. Heat till almost dry and transfer the solution into a 100-mL volumetric flask and make up to volume.0 mL concentrated hydrochloric acid (36 %) (digestion 2.Dilute 25 mL propanol-2 in some ultra pure water in a 500-mL volumetric flask and make up to volume. 6.1A or 6.Dissolve 1.2 Diluted Standard Solution. 7. Transfer the solution into a 100-mL volumetric flask. 6. Let cool down and make up to the mark with ultra pure water.5 Butanol.3). CALIBRATION AND STANDARDS 7.5 mL concentrated nitric acid (65 %) and heat to dissolve.2) into 100-mL volumetric flasks which already contain 40 mL ultra pure water.4) or 1.00 – 5.20 g palladium(II) chloride in 0. Pb(NO3)2 may absorb water on standing. blanks and sample digests into polythene cups that fit in the automatic sampler of the atomic absorption . Determination of lead 6. The reagent should be standardised by titration with EDTA at pH 10 in the presence of tartrate ions with Eriochrome Black T as an indicator.Dilute 34. PROCEDURE 8. 8.3 Nitric Acid Solution 5 mol/L .7 mL concentrated nitric acid (65 %) in about 30 mL ultra pure water in a 100-mL volumetric flask. 6.00 mL of the diluted standard solution (6.p.2 Calibration Curve .00 mL of the standard series.00 – 4.6 Acidified Triton-X 100 Solution 1 % .3) and make up to volume.00 g triton-X in about 20 mL ultra pure water. add 20 mL nitric acid solution (6. 3.00 mL stock solution (6.0 mL concentrated nitric acid (65 %) (digestion 2.00 – 3. 6. Remark: 2. Pb concentration 1 mg/L .Dissolve 1. Pb concentration 1000 mg/L .

. 7. Remarks: 3.2 % palladium chloride in 5 % butanol as matrix modifier is necessary. the optimum temperature values to be set may differ from the values given above.7 - 7 2100 2.Determinations.0 Ar 6 2100 0. Put standards.0 Ar Ar = argon.HF . Parameters Pb Settings lamp current 5 mA Wavelength 283. Pipette 1 mL of the matrix modifier (6. Add 0. in order to achieve more reproducible drying conditions in the graphite atomiser (Temminghoff. Butanol (0. For using the given temperature program 0. The operating parameters and temperature programme are given below.5 nm Measurement mode peak area Replicates 3 Temperature program Step Temp (°C) Time (s) Sheath gas 1 95 5.0 Ar/H2 5 800 2.0 Ar/H2 4 800 5. to 1 mL of the Pd solution. For other digestion procedures the temperature program should be optimised. The wash solution of the automatic sampler contains a 5 % propanol-2 solution (6.05 mL of the acidified triton-X solution (6.0 Ar/H2 3 800 5. The relative standard deviation should be less than 2 % for three replicates.7) in order to lower its surface tension and to prevent growth of bacteria. The present method was worked out using a Varian SpectrAA-300 atomic absorption spectrometer equipped with a graphite tube atomiser.6) and mix thoroughly with an electric mini-stirrer. The measurements can be performed with any ETA-AAS system. Every sample should be measured at least three times and for calculation the mean can be used. Pyrolytically coated partition tubes are used in the author's laboratory.05 mL of butanol (6. such settings may differ even within two instruments of the same type and should be always checked out experimentally. The sample volume which is injected is 20 µL and of the matrix modifier 5 µL.4) into another cup.3 nm slit width 0. Samples with high iron content may give too low results when applying a deuterium background correction system (Van der Lee et al. When using other instruments or matrix modifiers.4 (HNO3 .H2O2). modifier. blanks and sample digests in the appropriate place of the sampler. Heat in a graphite furnace according to an appropriate time-temperature programme (see remarks 6 and 7).4 M HNO3 (see remark 7). 4. before use. an automatic sampler and a Zeeman-effect background correction system and for a matrix of 0. The temperatures mentioned are instrument settings instead of real temperature values. 5.0 - 8 2500 0. 1990).3 nm in the atomisation phase (use background correction).3 - 9 2500 3. Determination of lead 155 spectrophotometer. . 1987). 6.0 Ar/H2 2 130 40. add 0.5) and mix. Ar/H2 = 95 % argon and 5 % hydrogen The temperature program given here is for the digestion procedure 2.05 mL) is added. Measure the absorbance at 283.

Temminghoff.1 The total lead content in the dried plant material. E. expressed in µg/kg Pb. Appl. Determination of lead 9. At. Anal. Spectrosc.M. in mL.1 Van der Lee. in Pg/L. .J. Spectrom. Novozamsky. J. Signal stabilisation in Electrothermal Atomisation Atomic Absorption Spectrometry by means of addition of butanol. w is the weight of plant material sample. 1987. V.M. J.. 10.J.J. E. CALCULATION 9. V is the total volume of digest at the end of the digestion procedure. in g. in Pg/L. 10. 41: 388-390.b) * V / w in which: a is the concentration of lead in the sample digest.G.J. is calculated by: (a .2 Temminghoff. Houba and I. 1990.156 Determinations. REFERENCES 10. b is the concentration of lead in the blank digest. Background corrections in the determination of Cd and Pb by flame AAS in plant and soil samples with high Fe levels. 5: 273.

Pb concentration 1000 mg/L .D DETERMINATION OF LEAD BY ICP-MS 1. PRECISION AND ACCURACY 4. at reasonable control and thorough sample preparation. and quantified with a channel electron multiplier. and 208 amu. 3.1 This procedure yields a standard curve that is linear up to approximately 50 Pg/L Pb.) in a 1000-mL polythene volumetric flask which already contains about . where all components are vaporised.HF).04 µg/L in the digest. Pb(NO3)2.1 Inductively coupled plasma mass spectrometer. 1. 5. 6.12 µg/L (13 respectively 40 µg/kg in the dried plant material). RANGE AND DETECTION LIMIT 2. REAGENTS 6. sorted according to their mass-to-charge ratios. Make up to 1000 mL with ultra pure water.1 The reproducibility of determinations by this procedure should give. The determination limit is approximately 0. 4.2 This determination may be carried out on digest 2.5985 g lead nitrate. Pb concentration 1000 mg/L . 6. digest 2.H2O2 .1 No interferences are expected.7 (digestion by dry-ashing followed by treatment with HF). Pb concentration 1 mg/L .1B Stock Solution. PRINCIPLE OF THE METHOD 1.18. a coefficient of variation within 10 %.1 Solutions with lead compounds are nebulised into an argon plasma.H2O2 .2 The detection limit is approximately 0.2 Standard Solution. 2. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer.HF) and digest 2.p.1A Stock Solution. 6.Dissolve 1. Determination of lead 157 4.02607. Lead is determined by the sum of mass 206. APPARATUS 5. 2. 207.Pipette 1 mL concentrated nitric acid (65 % s.Merck nr 1. in some ultra pure water in a volumetric flask of 1000 mL.Determinations. INTERFERENCES 3.4 (digestion with HNO3 .3 (microwave digestion with HNO3 .

in Pg/L.pipette 0 – 1. PROCEDURE 8. and 208 amu. in g.1B) and make up to volume with ultra pure water. 207.2) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks.1 The total lead content in the dried plant material. Remarks: 3. In this way the measurements are checked continuously and the data output is in concentration units in the extracts. The reagent should be standardised by titration with EDTA at pH=10 in the presence of tartrate ions with Eriochrome Black T as an indicator. 8.7).The counts per second are plot versus Pg/L lead in the standard series. the blanks and the sample digests the Pb concentration with the ICP-MS by the sum of mass 206. Mn.1 Measurement – Measure in the standard series. Co. CALCULATION 9. expressed in µg/kg Pb. A mix standard series can be used for simultaneous measurements with ICP-MS (Al. This standard series has Pb concentrations of 0 –10 – 20 – 50 µg/L.00 – 5.3). w is the weight of plant material sample. Add either 1. 4. Remark: 1. Ni. V and Zn).3 mL concentrated nitric acid (65 %) (digestion 2. A data management system and system controller are used. CALIBRATION AND STANDARDS 7. . Determination of lead 500 mL ultra pure water.4) or 0. 7.1A or 6. Cu. Sn.158 Determinations. in Pg/L. b is the concentration of lead in the blank digest. is calculated by: (a . Sb. Let cool down and make up to the mark with ultra pure water.2 Calibration Curve .00 mL stock solution (6.00 – 2. Remark: 2.1 mL concentrated hydrochloric acid (36 %) (digestion 2.0 mL concentrated nitric acid (65 %) (digestion 2.b) * V / w in which: a is the concentration of lead in the sample digest. V is the total volume of digest at the end of the digestion procedure. in mL. Pb. Add 1. Cd.00 mL of the standard solution (6. As a check all standards can be measured as samples. Pb(NO3)2 may absorb water on standing. Cr.1 Standard Series . 9. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series. 7. As. 0.

PRECISION AND ACCURACY 4.4 (digestion with HNO3 . where all components are vaporised. digest 2. Transfer 3 ampoules of 1000 mg/L SO42.1 No interferences are expected.H2O2 .1 This procedure yields a standard curve that is linear up to at least 80 mg/L S. The determination limit is approximately 0. Determination of sulphur fractions 159 4. a coefficient of variation within 10 %. 6. 3.19 DETERMINATION OF SULPHUR FRACTIONS 4.Dissolve 5.Determinations. RANGE AND DETECTION LIMIT 2.5 respectively 1. 1. 4.1 Inductively coupled plasma optical emission spectrometer. K2SO4 (see remark 1).H2O2 . at reasonable control and thorough sample preparation. S concentration 1000 mg/L . 6.19. REAGENTS 6. Sulphur compounds are dissociated and excited.09872.1A Stock Solution.3 (microwave digestion with HNO3 .1B Stock Solution.05 mg/L in the digest. . 5.1 The reproducibility of determinations by this procedure should give.5 (digestion with HNO3).2 The detection limit is approximately 0.2 This determination may be carried out on digest 2.HF). PRINCIPLE OF THE METHOD 1.1 Solutions with sulphur compounds are nebulised into an argon plasma. 2. APPARATUS 5.HF) and digest 2.a 1000-mL volumetric flask and make up to volume with water. S concentration 1000 mg/L – Merck nr 1.14 mg/L (0.972 nm.A DETERMINATION OF TOTAL SULPHUR BY ICP-OES 1.5 mmol/kg in the dried plant material). in some water in a 1000-mL volumetric flask and make up to volume. 2.4398 g potassium sulphate. INTERFERENCES 3. and then emit radiation of which the intensity is measured at a wavelength of 181.

7.5 mL concentrated nitric acid (65 %) (digestion 2.861 nm. After the recommended heating procedure.1 Standard Series . 4. Mg. any lumps should be cut down so that only fine crystals remain. P. the blanks and sample digests the S concentration with an ICP-OES at a wavelength of 181. PROCEDURE 8.Pipette 0 – 1.The emission counts are plot versus mg/L sulphur in the standard series. Na.Measure in the standard series. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. In this way the measurements are checked continuously and the data output is in concentration units in the extracts. Add either 10 mL concentrated nitric acid (65 %) (digestion 2.03119 * (a . Cr. Fe. The dried potassium sulphate should be weighed as soon as it has reached the ambient temperature. 8. At this wavelength a (fitted) background correction is used. is calculated by: 0. A data management system and system controller are used. 7. K.1 The total sulphur content of the dried plant material. This standard series has S concentrations of 0 – 10 – 20 – 80 mg/L. Just before drying.160 Determinations. Co. 9. 3. The potassium sulphate has to be dried at 200 °C for at least 24 hours just before weighing.5). Remark: 2. The fine crystals should.00 – 8.4) or 1. at a wavelength of 234. CALIBRATION AND STANDARDS 7. Determination of sulphur fractions Remark: 1. Mn. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on.00 mL of the stock solution (6. As a check all standards can be measured as samples. Remarks: 3.2 Calibration Curve .1A or 6. A mix standard series can be used for simultaneous measurements with ICP-OES (Al. 5.972 nm.00 – 2. CALCULATION 9. Beryllium (5 mg/L).b) * V / w . the potassium sulphate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series.1B) into 100-mL volumetric flasks which already contain 40 mL water.3). S and Zn). Ca.0 mL concentrated nitric acid (65 %) (digestion 2. however. expressed in mmol/kg S. is used in the author's laboratory as an internal standard to compensate for matrix effects.1 Measurement . Allow cooling and make up to volume. Cd. Cu. This is important.

in mg/L. in mg/L. 1986. van der Lee. Soil Sci. in mL.J. Houba and E.1 Novozamsky. Determination of sulphur fractions 161 in which: a is the concentration of sulphur in the sample digest. I.J.G. J.J.. 10.M. V. b is the concentration of sulphur in the blank digest. w is the weight of plant material sample.Determinations. V is the total volume of digest at the end of the digestion procedure. Determination of total sulphur and extractable sulphate in plant materials by inductively-coupled plasma atomic emission spectrometry. Plant Anal. Commun. R. . in g. Temminghoff. van Eck. 17: 1147-1157. REFERENCES 10.

APPARATUS 5. 6.19. 2. S concentration 1000 mg/L . Determination of sulphur fractions 4.1 (extraction with water). 3. 2. S concentration 1000 mg/L .1 This procedure yields a standard curve that is linear up to at least 80 mg/L S. in some water in a 1000-mL volumetric flask and make up to volume. PRECISION AND ACCURACY 4.4398 g potassium sulphate. K2SO4 (see remark 1).1 No interferences are expected.1 Inductively coupled plasma optical emission spectrometer. INTERFERENCES 3.1A Stock Solution. at reasonable control and thorough sample preparation.05 mg/L in the extract. 5.162 Determinations.1 Sulphate ions in the extracts are precipitated by barium ions. The determination limit is approximately 0.B DETERMINATION OF SULPHATE BY ICP-OES 1. RANGE AND DETECTION LIMIT 2.1B Stock Solution. 5.2 Centrifuge with swing-out head. Sulphate ions decompose. PRINCIPLE OF THE METHOD 1.to a 1000-mL volumetric flask and make up to volume with water. The solution is then nebulised into an argon plasma. 6.5 respectively 1. the sulphur atoms thus formed are excited and then emit radiation of which the intensity is measured at a wavelength of 181. 1.09872. . the barium sulphate precipitate is dissolved by EDTA.2 This determination may be carried out on extract 3.Dissolve 5. After a clean up.1 The reproducibility of determinations by this procedure should give. Transfer 3 ampoules of 1000 mg/L SO42.Merck nr 1.2 The detection limit is approximately 0.972 nm. 4.5 mmol/kg in the dried plant material). a coefficient of variation within 10 % + 10 mmol/kg. REAGENTS 6.15 mg/L (0. where all components are vaporised.

The dried potassium sulphate should be weighed as soon as it has reached the ambient temperature. add 5.1B) into 100-mL volumetric flasks. add 5. Bring the tubes two by two with water at the same weight. 7.91 g/cm3). Make up to the mark with EDTA solution (6. preferably overnight but at least during 2 hours. 6. Determination of sulphur fractions 163 6. the blanks and the sample extracts into these tubes. Next. any lumps should be cut down so that only fine crystals remain.3).Pipette 0 – 1.0 mL of EDTA solution (6. 8. swirl now and then.2 Standard Solution.3 Barium Chloride Solution 1 mol/L .00 – 2. Carefully decant the supernatant. because coarse crystals contain much occluded water in their cavities and thus would need a higher drying temperature. H4EDTA.0 mL of the standard series.0 mL of barium chloride solution (6. .00 mL of the stock solution (6. S concentration 400 mg/L . and centrifuge for 10 min at 1200-1500 g. NH4OH (U = 0.Determinations.Dissolve 5. Finally.1 Standard Series . Just before drying.Weigh a series of 15-mL centrifuge tubes (empty weight e gram per tube).1A or 6.5 mL of liquid will remain in the tube. Add to each tube 1. The potassium sulphate has to be dried at 200 °C for at least 24 hours just before weighing. so that the precipitate and only about 0.4) and shake to bring the precipitate into suspension.Pipette 40 mL stock solution (6.The emission counts are plot versus mg/L sulphur in the standard series. in 30 mL concentrated aqueous ammonia. After the recommended heating procedure. the potassium sulphate should be cooled in a desiccator containing preferably magnesium perchlorate as a desiccant. This standard series has S concentrations of 0 – 10 – 20 – 80 mg/L.00 – 8. Remark: 1. CALIBRATION AND STANDARDS 7.0 mL of water and repeat the shaking and the centrifuging.1B) in a 100-mL volumetric flask and make up to volume. Allow the precipitate to dissolve completely. Make up to 1 litre with water.2H2O. The fine crystals should. in about 600 mL water.3). This is important. 7. 6.1A or 6. Add 82 mL concentrated hydrochloric acid (36 %) and make up to 1 litre. and mix by shaking.1 Separation of sulphate . Decant again the supernatant and weigh the tube (c gram) in order to establish the volume of liquid left behind. PROCEDURE 8. BaCl2.2 Calibration Curve .Dissolve 244 g barium chloride dihydrate.84 g ethylene diamine tetra acetic acid. Then pipette 5.2 EDTA Solution 0.02 mol/L . however. not be pulverised because this enhances deliquescence (= attraction of water) and/or efflorescence (= weathering) later on.

A data management system and system controller are used. As a check all standards can be measured as samples. J. van Eck. Beryllium (5 mg/L).2 Measurement .G. in g. R. the blanks and the sample extracts the sulphate-sulphur concentration with an ICP-OES at a wavelength of 181.861 nm. 1986. w is the weight of plant material sample. 3. in mg/L.J.e) / 5 * 0. 5. At this wavelength a (fitted) background correction is used.. expressed in mmol/kg S- SO4. V. .M. I. 10. in mg/L. Houba and E.1 Novozamsky. Commun.972 nm. a is the concentration of sulphate-sulphur in the plant material digest.1 The sulphate-sulphur content in the dried plant material.164 Determinations. is calculated by: (5 + c .03119 * (a .b) * V / w in which: c is weight of centrifuge tube with remaining liquid. Determination of total sulphur and extractable sulphate in plant materials by inductively coupled plasma atomic emission spectrometry. 9. In this way the measurements are checked continuously and the data output is in concentration units in the extracts. Determination of sulphur fractions 8. CALCULATION 9. 17: 1147-1157. van der Lee.Measure in the standard series. in g. The calculation should be amended accordingly.J. Remarks: 2. REFERENCES 10. e is weight of empty centrifuge tube. Temminghoff. V is the total volume of water taken for extraction. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series. in g. at a wavelength of 234. Soil Sci.J. is used in the author's laboratory as an internal standard to compensate for matrix effects. b is the concentration of sulphate-sulphur in the sample extract. 4. To measure low concentrations of sulphate sulphur in the sample extracts a 1:1 dilution of the extract with EDTA can be used instead of the 1:5 dilution. Plant Anal. in mL.

Merck nr 1. REAGENTS 6. PRECISION AND ACCURACY 4.1 Stock Solution.1 This procedure yields a standard curve that is linear up to approximately 50 Pg/L Sb. INTERFERENCES 3. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer. a coefficient of variation within 10 %. 6.7 (digestion by dry-ashing followed by treatment with HF).p.005 µg/L in the digest. RANGE AND DETECTION LIMIT 2. at reasonable control and thorough sample preparation.1 Solutions with antimony compounds are nebulised into an argon plasma. 3. The determination limit is approximately 0. where all components are vaporised.02601.4 (digestion with HNO3 . APPARATUS 5.HF).Determinations.2 The detection limit is approximately 0.H2O2 . and quantified with a channel electron multiplier.A DETERMINATION OF ANTIMONY BY ICP-MS 1. Antimony is determined at mass 121 amu.HF) and digest 2. 2.Pipette 1 mL concentrated nitric acid (65 % s. PRINCIPLE OF THE METHOD 1. 2. digest 2.2 Standard Solution.1 The reproducibility of determinations by this procedure should give. 5. Sb concentration 1 mg/L . sorted according to their mass-to-charge ratios.20 DETERMINATION OF ANTIMONY 4.3 (microwave digestion with HNO3 . Determination of antimony 165 4.2 This determination may be carried out on digest 2. 6. Sb concentration 1000 mg/L .1 Inductively coupled plasma mass spectrometer.015 µg/L (2 respectively 5 µg/kg in the dried plant material). 1.20.H2O2 .1 No interferences are expected 4.) in a 1000-mL polythene volumetric flask which already contains about .

As a check all standards can be measured as samples. A mix standard series can be used for simultaneous measurements with ICP-MS (Al. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series. Add either 1. V and Zn).4) or 0. b is the concentration of antimony in the blank digest.1 Standard Series . V is the total volume of digest at the end of the digestion procedure. CALCULATION 9. A data management system and system controller are used. 9. Cd. is calculated by: (a .b) * V / w in which: a is the concentration of antimony in the sample digest. In this way the measurements are checked continuously and the data output is in concentration units in the digests. Cu. in Pg/L.00 – 5. Mn.1 Measurement .2) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks. 0.00 mL stock solution (6. Remarks: 2. w is the weight of plant material sample. Remark: 1.1 mL concentrated hydrochloric acid (36 %) (digestion 2. . Ni.Measure in the standard series. PROCEDURE 8. Let cool down and make up to the mark with ultra pure water. in Pg/L. As.00 mL of the standard solution (6. in mL. 7.2 Calibration Curve . expressed in µg/kg Sb. CALIBRATION AND STANDARDS 7.The counts per second are plot versus Pg/L antimony in the standard series. in g.1) and make up to volume with ultra pure water.pipette 0 – 1. Cr. Determination of antimony 500 mL ultra pure water.0 mL concentrated nitric acid (65 %) (digestion 2. 7.00 – 2. the blanks and the sample digests the Sb concentration with the ICP-MS at a mass of 121 amu. Sb. 8.3).7). Sn. 3.166 Determinations.3 mL concentrated nitric acid (65 %) (digestion 2. Co. Pb. This standard series has Sb concentrations of 0 – 10 – 20 – 50 µg/L. Add 1.1 The total antimony content in the dried plant material.

where all components are vaporised. can be used because glass contains Si.2 The detection limit is approximately 0.3 Inductively coupled plasma optical emission spectrometer.5 mg/L in the extract. The determination limit is approximately 1.5 mg/L (16 respectively 50 mg/kg in the dried plant material). and then emit radiation of which the intensity is measured at a wavelength of 288. PRECISION AND ACCURACY 4. Determination of silicon 167 4.2 (extraction with HF . 5. INTERFERENCES 3.1 No interferences are expected. Silicon compounds are dissociated and excited. . a coefficient of variation within 10 % + 10 mg/kg.21 DETERMINATION OF SILICON 4. PRINCIPLE OF THE METHOD 1.HCl).Determinations. 5.1 The reproducibility of determinations by this procedure should give. The silicon content of the dried plant material should be higher than 500 mg/kg.A DETERMINATION OF SILICON BY ICP-OES 1. 5. fitted with HF-resistant nebuliser and inner torch tube. Only polythene flasks etc. RANGE AND DETECTION LIMIT 2.21. 3.1 Solutions with silicon compounds are nebulised into an argon plasma. Remark: 1. 2.158 nm.2 Polythene bottles. 2. 4.1 This procedure yields a standard curve that is linear up to at least 100 mg/L Si. at reasonable control and thorough sample preparation. 1.2 This determination is to be carried out on extract 3. APPARATUS 5.1 Polycarbonate test tubes + stoppers.3 Polythene volumetric flasks. 5.

Si concentration 1000 mg/L . nr 3740. Samples with Si concentrations beyond the standard series should be diluted first with acid mixture (6.0 M in HCl. having the same quality.e.Dilute 75 mL of concentrated aqueous ammonia (25 %) with water to 250 mL. pipette tips etc. Remarks: 4.LPS Benelux art. The dilution for the standards and samples must be done with ultra pure water of one batch. at a wavelength of 234. For this determination. See remark 5.1 Stock Solution. New polycarbonate test tubes. A mix standard series can be used for simultaneous measurements with ICP-OES (B and Si). the blanks and the sample extracts the Si concentration with the ICP-OES at a wavelength of 251.1) in 100-mL polythene volumetric flasks. 6.1 Standard Series . safety goggles and protective cloths.1.0 M in HF and 2.168 Determinations.Pipette 0 – 5.861 nm. 5.1 Measurement .Dilute.. Remarks: 2. Beryllium (5 mg/L). 7. If any HF comes into contact with the skin. Determination of silicon 6. 6. is used in the author's laboratory as an internal standard to compensate for matrix effects. add 50 ml acid mixture (6.2 Calibration Curve . CALIBRATION AND STANDARDS 7. because new material may release silicon. This standard series has Si concentrations of 0 – 50 – 100 mg/L. Remarks: 5. 6. 7. REAGENTS 6. wash immediately and thoroughly with water and thereafter dab with 4 M ammonia (4.2).61 nm. 3. Measure in the standard series. since demineralised water may contain varying amounts of Si. . using piston-type pipettes or a diluting apparatus with polythene tips the standard series.2) and then follow the procedure with the usual 1:20 dilution. the blanks and the sample extracts 1 + 19 (v/v) with ultra pure water in polycarbonate test tubes and mix. all solutions must be prepared with ultra pure water.2) and make up to volume with ultra pure water. 8. (This solution is 9.2 Acid mixture .The emission counts are plot versus mg/L silicium in the standard series.4) or calcium gluconate gel. must be cleaned by rinsing with the acid mixture (6.3 Ammonia Solution 4 mol/L . PROCEDURE 8. 7.00 – 10. i. Hydrofluoric acid is a treacherous skin poison.Mix 150 mL of concentrated hydrofluoric acid (40 %) with 60 mL of concentrated hydrochloric acid (36 %) and add 165 mL ultra pure water.00 mL stock solution (6. Work in a good fume hood and wear rubber gloves.

b is the concentration of silicon in the blank extract. V is the volume of acid mixture used for extraction. van Eck and V. R.. w is the weight of plant material sample.1 The silicon content of the dried plant material.b) * V / w in which: a is the concentration of silicon in the sample extract. Soil Sci. 15: 205-211. CALCULATION 9. . expressed in mg/kg Si. in mL. A rapid determination of silicon in plant material. 1984.G. Determination of silicon 169 9. in mg/L. Houba. Commun. is calculated by: (a . 10.1 Novozamsky. I. in g. in mg/L.J.Determinations.. REFERENCES 10. Plant Anal.

INTERFERENCES 120 120 78 3.08 µg/L in the digest. 2. The determination limit is approximately 0.H2O2 . 2.1 Te has the same mass as Sn. where all components are vaporised. A correction factor can be applied.7 (digestion by dry-ashing followed by treatment with HF).1 Inductively coupled plasma mass spectrometer. sorted according to their mass-to-charge ratios and quantified with a channel electron multiplier. 5.HF) and digest 2. at reasonable control and thorough sample preparation.22.02671. Se40Ar 118 80 40 molecule has the same mass as Sn whereas Se Ar has the same mass as 120 Sn.HF).170 Determinations.22 DETERMINATION OF TIN 4. a coefficient of variation within 10 %. digest 2. PRINCIPLE OF THE METHOD 1. PRECISION AND ACCURACY 4. Sn concentration 1000 mg/L .1 The reproducibility of determinations by this procedure should give. Determination of tin 4. 6. 3.4 (digestion with HNO3 . RANGE AND DETECTION LIMIT 2.2 This determination may be carried out on digest 2. .3 (microwave digestion with HNO3 . APPARATUS 5. REAGENTS 6.A DETERMINATION OF TIN BY ICP-MS 1.1 This procedure yields a standard curve that is linear up to at least 50 Pg/L Sn.2 The detection limit is approximately 0.1 Stock Solution. 1. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer.1 Solutions with tin compounds are nebulised into an argon plasma. Tin is determined at mass 120 amu.H2O2 .Merck nr 1.23 µg/L (27 respectively 80 µg/kg in the dried plant material). 4.

p. Let cool down and make up to the mark with ultra pure water.1) and make up to volume with ultra pure water. Mn.pipette 0 – 1. in g. Add 1.2) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks.00 mL of the standard solution (6.0 mL concentrated nitric acid (65 %) (digestion 2. A mix standard series can be used for simultaneous measurements with ICP-MS (Al. in Pg/L.3 mL concentrated nitric acid (65 %) (digestion 2. in Pg/L. the blanks and the sample digests the Sn concentration with the ICP-MS at a mass of 120 amu. Cr.1 Standard Series .1 Measurement – Measure in the standard series. Pb.1 mL concentrated hydrochloric acid (36 %) (digestion 2. 3.2 Calibration Curve . This standard series has Sn concentrations of 0 –10 – 20 – 50 µg/L.2 Standard Solution. As a check all standards can be measured as samples. V and Zn).Determinations. b is the concentration of tin in the blank digest. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series. w is the weight of plant material sample.00 – 2. in mL. CALCULATION 9. is calculated by: (a . Co. Cd.4) or 0. PROCEDURE 8. 9. Sn concentration 1 mg/L . V is the total volume of digest at the end of the digestion procedure. 7.7). 0.00 – 5. Add either 1.00 mL stock solution (6. 8.1 The total tin content in the dried plant material. Sn. A data management system and system controller are used.Pipette 1 mL concentrated nitric acid (65 % s. Ni.The counts per second are plot versus Pg/L tin in the standard series.3). Determination of tin 171 6. In this way the measurements are checked continuously and the data output is in concentration units in the digests. CALIBRATION AND STANDARDS 7. Remarks: 2.) in a 1000-mL polythene volumetric flask which already contains about 500 mL ultra pure water. Remark: 1. As. Sb.b) * V / w in which: a is the concentration of tin in the sample digest. Cu. expressed in µg/kg Sn. . 7.

005 µg/L in the digest. Add 1.7 (digestion by dry-ashing followed by treatment with HF). Determination of vanadium 4. REAGENTS 6.1) and make up to volume with ultra pure water.1 This procedure yields a standard curve that is linear up to at least 50 Pg/L V. 4. PRECISION AND ACCURACY 4.Pipette 1 mL concentrated nitric acid (65 % s.2 Standard Solution.4 (digestion with HNO3 . V concentration 1 mg/L .p. APPARATUS 5.3 (microwave digestion with HNO3 . 3.1 The reproducibility of determinations by this procedure should give.H2O2 .A DETERMINATION OF VANADIUM BY ICP-MS 1.172 Determinations. 6.23.) in a 1000-mL polythene volumetric flask which already contains about 500 mL ultra pure water. 6. INTERFERENCES 3.23 DETERMINATION OF VANADIUM 4.1 Interferences are expected for 34S16O1H and 35Cl16O due to mass overlap with 51V.H2O2 .Merck nr 1. 1. digest 2.1 Stock Solution. 2.HF) and digest 2. .1 Inductively coupled plasma mass spectrometer. 5. at reasonable control and thorough sample preparation. a coefficient of variation within 10 %. 2.015 µg/L (2 respectively 5 µg/kg in the dried plant material).2 The detection limit is approximately 0. sorted according to their mass-to-charge ratios and quantified with a channel electron multiplier. PRINCIPLE OF THE METHOD 1. Vanadium is determined at mass 51 amu.02666.HF). where all components are vaporised. The ions produced are entrained in the plasma gas and introduced into a mass spectrometer. V concentration 1000 mg/L .00 mL stock solution (6. RANGE AND DETECTION LIMIT 2. The determination limit is approximately 0.2 This determination may be carried out on digest 2.1 Solutions with vanadium compounds are nebulised into an argon plasma.

7). Pb. Remark: 1. Add either 1.Determinations.1 mL concentrated hydrochloric acid (36 %) (digestion 2.00 mL of the standard solution (6. Determination of vanadium 173 7. Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series. Sb. Remarks: 2.3).2) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks. Let cool down and make up to the mark with ultra pure water. Make use of corrections if necessary. Mn. CALIBRATION AND STANDARDS 7. Cr.2 Calibration Curve . This standard series has V concentrations of 0 –10 – 20 – 50 µg/L. As a check all standards can be measured as samples. PROCEDURE 8.pipette 0 – 1. CALCULATION 9. 7. b is the concentration of vanadium in the blank digest. A mix standard series can be used for simultaneous measurements with ICP-MS (Al. w is the weight of plant material sample. Ni.00 – 2.4) or 0. is calculated by: (a . V is the total volume of digest at the end of the digestion procedure. 3. Co. 0.1 Measurement .The counts per second are plot versus Pg/L vanadium in the standard series. in g. the blanks and the sample digests the V concentration with the ICP-MS at a mass of 51 amu. in Pg/L. In this way the measurements are checked continuously and the data output is in concentration units in the digests.1 Standard Series .b) * V / w in which: a is the concentration of vanadium in the sample digest. Sn. As. Cd. . expressed in µg/kg V. A data management system and system controller are used.Measure in the standard series. in mL. V and Zn).00 – 5.0 mL concentrated nitric acid (65 %) (digestion 2. Cu.1 The total vanadium content in the dried plant material.3 mL concentrated nitric acid (65 %) (digestion 2. in Pg/L. 8. 9.

Zn concentration 1000 mg/L .H2O2 . Determination of zinc 4.5 mg/kg in the dried plant material). The determination limit is approximately 0.9 nm. PRECISION AND ACCURACY 4. digest 2.2 This determination may be carried out on digest 2.HClO4 .06 mg/L (3. using deuterium background correction.7 (digestion by dry-ashing followed by treatment with HF).19806.3 (microwave digestion with HNO3 .1 The sample is nebulised into an air-acetylene flame. 2.Merck nr 1. REAGENTS 6.174 Determinations.salicylic acid . at reasonable control and thorough sample preparation.HF).24.6 (digestion with HNO3 .8 mg/L Zn. digest 2.02 mg/L in the digest. 4. background correction is necessary.1 (digestion with H2SO4 . APPARATUS 5.salicylic acid . The absorbance is measured at a wavelength of 213. 1.Se).1 The reproducibility of determinations by this procedure should give.2 The detection limit is approximately 0.24 DETERMINATION OF ZINC 4.H2O2 .1 To avoid interferences as much as possible. 2. 3. 5.H2SO4) and digest 2. PRINCIPLE OF THE METHOD 1. INTERFERENCES 3.HF).2 (digestion with H2SO4 . RANGE AND DETECTION LIMIT 2.1 Flame atomic absorption spectrophotometer with a device for correcting background absorption. .4 (digestion with HNO3 - H2O2 . 6.0-7. digest 2. zinc compounds are atomised and the zinc atoms thus formed absorb radiation from a hollow cathode lamp.1 This procedure yields a standard curve that is linear to approximately 0.1A Stock Solution. where it is vaporised.A DETERMINATION OF ZINC BY FLAME AAS 1. a coefficient of variation within 5 % + 5 mg/kg. digest 2.H2O2).

3).4). This means that calculation by means of linear regression is not allowed.7H2O may lose crystal water on standing.5 mL concentrated sulphuric acid (96 %) (digestion 2. Determination of zinc 175 6.1A or 6.0 mL concentrated nitric acid (65 %) (digestion 2. Remark: 1. since these may release zinc. 8. 10 mL concentrated nitric acid (65 %) (digestion 2.1 or 2. PROCEDURE 8. Zn concentration 1000 mg/L . in g.00 – 4. w is the weight of plant material sample.Pipette 0 – 2. the blanks and the sample digests the Zn concentration with flame AAS at a wavelength of 213.00 – 10.2).2 Calibration Curve .1 Standard Series .4 – 0. is calculated by: (a .1 The total zinc content in the dried plant material. using a just blue (stoichiometric) air-acetylene flame. ZnSO4. 7. 7. in mg/L.398 g zinc sulphate heptahydrate.1 Measurement – Measure in the standard series.00 mL stock solution (6. expressed in mg/kg Zn.Dissolve 4.00 mL of the standard solution (6.0 mL concentrated hydrochloric acid (36 %) (digestion 2.7H2O.0 mg/L.00 – 8. ZnSO4. Zn concentration 20 mg/L . Remark: 2. . Remark: 3.00 – 6. CALIBRATION AND STANDARDS 7.1B Stock Solution. Add either 4. CALCULATION 9.Determinations. Let cool down and make up to the mark with water.2 Standard Solution. 9.1B) into a 100-mL volumetric flask and make up to volume. Use background correction.b) * V / w in which: a is the concentration of zinc in the sample digest.2) into 100-mL volumetric flasks which already contain 40 mL water.7).2 – 0. in mL.Pipette 2. The reagent should be standardised by titration with EDTA at pH 10 with Eriochrome Black T as an indicator. 3. in about 500 mL ultra pure water in a 1000-mL volumetric flask and make up to volume. b is the concentration of zinc in the blank digest. Do not use rubber stoppers.6 – 2.9 nm. This standard series has Zn concentrations of 0 - 0.2 – 1. in mg/L.6) or 1. 6.8 – 1. The calibration curve is slightly bent towards the x-axis.The absorbance (A) is plot versus mg/L zinc in the standard series.45 mL concentrated sulphuric acid (96 %) (digestion 2. 0. V is the total volume of digest at the end of the digestion procedure.

1 No interferences are expected. ZnSO4.Dissolve 4. Zinc compounds are dissociated and excited. REAGENTS 6.200 nm.1 Solutions with zinc compounds are nebulised into an argon plasma.0-7. 1.1B Stock Solution. 5. Determination of zinc 4.2 This determination may be carried out on digest 2.1A Stock Solution.4 (digestion with HNO3 . RANGE AND DETECTION LIMIT 2. 3. PRECISION AND ACCURACY 4.7 (digestion by dry-ashing followed by treatment with HF). PRINCIPLE OF THE METHOD 1.06 mg/L (3.1 This procedure yields a standard curve that is linear up to approximately 40 mg/L Zn. . in about 500 mL water in a 1000-mL volumetric flask and make up to volume. and then emit radiation of which the intensity is measured at a wavelength of 206. The determination limit is approximately 0.24.Merck nr 1. ZnSO4. Zn concentration 1000 mg/L . The reagent should be standardised by titration with EDTA at pH 10 with Eriochrome Black T as an indicator.7H2O may lose crystal water on standing. 4. digest 2.B DETERMINATION OF ZINC BY ICP-OES 1.1 The reproducibility of determinations by this procedure should give.H2O2 . where all components are vaporised.7H2O.19806.3 (microwave digestion with HNO3 .H2O2 . 6. Zn concentration 1000 mg/L .HF).5 mg/kg in the dried plant material). 2.2 The detection limit is approximately 0.1 Inductively coupled plasma optical emission spectrometer.398 g zinc sulphate heptahydrate. 2.176 Determinations.02 mg/L in the digest. at reasonable control and thorough sample preparation. 6. Remark: 1. a coefficient of variation within 5 % + 5 mg/kg. APPARATUS 5.HF) and digest 2. INTERFERENCES 3.

1B) into 100-mL volumetric flasks which already contain 40 mL water. PROCEDURE 8. Mg. As a check all standards can be measured as samples. Ni. Cr. b is the concentration of zinc in the blank digest. 3. Fe. Remark: 2. Remarks: 3. Scandium (5 mg/L). 9. in mg/L.0 – 2. V is the total volume of digest at the end of the digestion procedure. This standard series has Zn concentrations of 0 – 1.235 nm. 8. At this wavelength a (fitted) background correction is used.b) * V / w in which: a is the concentration of zinc in the sample digest.0 mg/L. K.0 – 40.Measure in the standard series. is calculated by: (a .1 Standard Series . Determination of zinc 177 7. Na.1 The total zinc content in the dried plant material. 7. Ca. Mn. 5. is used in the author's laboratory as an internal standard to compensate for matrix effects. A data management system and system controller are used. in mL.7). 4.Pipette 0 – 0. CALCULATION 9.4) or 1. at a wavelength of 255. S and Zn). Cd. Co. Let cool down and make up to the mark with water.The emission counts are plot versus mg/L zinc in the standard series. w is the weight of plant material sample.0 mL concentrated nitric acid (65 %) (digestion 2. . Add either 10 mL concentrated nitric acid (65 %) (digestion 2. in g.0 mL concentrated hydrochloric acid (36 %) (digestion 2.1A or 6. CALIBRATION AND STANDARDS 7.10 – 0. Due to the linearity of the ICP-OES it is possible to calibrate the ICP-OES only with the highest and zero standard of the standard series.00 mL of the stock solution (6.2 Calibration Curve . the blanks and the sample digests the Zn concentration with the ICP-OES at a wavelength of 213. In this way the measurements are checked continuously and the data output is in concentration units in the digests.3). P. Cu. expressed in mg/kg Zn. A mix standard series can be used for simultaneous measurements with ICP-OES (Al.856 nm.Determinations.20 – 4.1 Measurement . in mg/L.

Ce . Ba . 34S16O2. 6.2 Standard Solution.5 mg/kg in the dried plant material). Zn concentration 1000 mg/L .02670.3 (microwave digestion with HNO3 .1 This procedure yields a standard curve that is linear up to at least 50 Pg/L Zn.5 µg/L in the digest. The determination limit is approximately 4.4 (digestion with HNO3 .HF). Make up to 1000 mL with ultra pure water. a coefficient of variation within 10 %. Determination of zinc 4. at reasonable control and thorough sample preparation.HF) and digest 2.398 g zinc sulphate heptahydrate.5 respectively 1.Pipette 1 mL concentrated nitric acid (65 % s. digest 2. 5.H2O2 .178 Determinations. Zinc is determined at mass 66 or 68 amu.7 (digestion by dry-ashing followed by treatment with HF). REAGENTS 6. 2. in some ultra pure water in a 1000-mL volumetric flask.2 This determination may be carried out on digest 2. and quantified with a channel electron multiplier.) in a 1000-mL polythene volumetric flask which already contains about .1B Stock Solution. PRECISION AND ACCURACY 4.24.p. INTERFERENCES 3. Zn concentration 1000 mg/L .1 The reproducibility of determinations by this procedure should give. APPARATUS 5. RANGE AND DETECTION LIMIT 2. 132 Ba++ due to mass overlap at 66 136 ++ 136 Zn. 1. 6. 2.Merck nr 1. 6. Ar N2. ZnSO4.1 Solutions with zinc compounds are nebulised into an argon plasma. 3.H2O2 .2 The detection limit is approximately 1. where all components are vaporised.1A Stock Solution.Dissolve 4. Fe N show mass overlap at 68Zn. sorted according to their mass-to-charge ratios.C DETERMINATION OF ZINC BY ICP-MS 1.1 Inductively coupled plasma mass spectrometer.1 Interferences can be expected from 50Ti16O. Zn concentration 1 mg/L . The ions produced are entrained in the plasma gas and introduced into a mass spectrometer. ++ 40 14 54 14 4.5 µg/L (0. PRINCIPLE OF THE METHOD 1.7H2O.

Sb. 0. 9. A mix standard series can be used for simultaneous measurements with ICP-MS (Al.3). Let cool down and make up to the mark with ultra pure water.Determinations. Ni. is calculated by: 0. in Pg/L. CALCULATION 9.1 mL concentrated hydrochloric acid (36 %) (digestion 2. Co. Cu.b) * V / w in which: a is the concentration of zinc in the sample digest.4) or 0.00 mL of the standard solution (6.7). Due to the linearity of the ICP-MS it is possible to calibrate the ICP-MS only with the highest and zero standard of the standard series. This standard series has Zn concentrations of 0 –10 – 20 – 50 µg/L.00 – 2. in g. Cr.1B) and make up to volume with ultra pure water. .2 Calibration Curve . in mL. expressed in mg/kg Zn. Make use of corrections if necessary. Determination of zinc 179 500 mL ultra pure water.1 Standard Series . b is the concentration of zinc in the blank digest.The counts per second are plot versus Pg/L zinc in the standard series.pipette 0 – 1. CALIBRATION AND STANDARDS 7.3 mL concentrated nitric acid (65 %) (digestion 2. 4. As a check all standards can be measured as samples. Remarks: 3. V is the total volume of digest at the end of the digestion procedure. in Pg/L. A data management system and system controller are used.7H2O may lose crystal water on standing. ZnSO4.0 mL concentrated nitric acid (65 %) (digestion 2. As.001*(a . Mn. Cd. Sn. The reagent should be standardised by titration with EDTA at pH=10 with Eriochrome Black T as an indicator. Pb. Remark: 1. Measure in the standard series. Add either 1. 8. 7. In this way the measurements are checked continuously and the data output is in concentration units in the digests.1 Measurement . PROCEDURE 8.1 The total zinc content in the dried plant material.00 – 5. Remark: 2. 7. w is the weight of plant material sample.1A or 6.Dilute the blanks and the sample digests 1 + 9 (v/v) with ultra pure water and mix. V and Zn).00 mL stock solution (6. the blanks and the sample digests the Zn concentration with the ICP-MS at a mass of 66 or 68 amu. Add 1.2) in about 40 mL ultra pure water in a 100-mL polythene volumetric flasks.