1、BRITISH STANDARDBS EN ISO 17852:2008 BS 6068-2.98:2006Water quality Determination of mercury Method using a combined preservation and digestion step followed by atomic fluorescence spectrometryICS 13.060.50g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g4
2、9g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS EN ISO 17852:2008This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 June 2006 BSI 2008ISBN 978 0 580 59128 0National forewordThis Bri
3、tish Standard is the UK implementation of EN ISO 17852:2008. It is identical with ISO 17852:2006. It supersedes BS EN 13506:2002 and BS ISO 17852:2006, which are withdrawn.The title of this British Standard has been extended from the reference document to reflect the applicability of this method.The
4、 UK participation in its preparation was entrusted by Technical Committee EH/3, Water quality, to Subcommittee EH/3/2, Physical, chemical and biochemical methods.A list of organizations represented on this subcommittee can be obtained on request to its secretary.This publication does not purport to
5、include all the necessary provisions of a contract. Users are responsible for its correct application. Compliance with a British Standard cannot confer immunity from legal obligations.Amendments/corrigenda issued since publicationDate Comments30 June 2008 This corrigendum renumbers BS ISO 17852:2006
6、 as BS EN ISO 17852:2008EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN ISO 17852January 2008ICS 13.060.50 Supersedes EN 13506:2001 English VersionWater quality - Determination of mercury - Method using atomicfluorescence spectrometry (ISO 17852:2006)Qualit de leau - Dosage du mercure - Mthode par
7、spectromtrie de fluorescence atomique (ISO 17852:2006)Wasserbeschaffenheit - Bestimmung von Quecksilber -Verfahren mittels Atomfluoreszenzspektrometrie (ISO17852:2006)This European Standard was approved by CEN on 8 December 2007.CEN members are bound to comply with the CEN/CENELEC Internal Regulatio
8、ns which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the CEN Management Centre or to any CEN member.This Europea
9、n Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as theofficial versions.CEN members are the national
10、 standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United
11、 Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2008 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN ISO 17852:2008: EF
12、oreword The text of ISO 17852:2006 has been prepared by Technical Committee ISO/TC 147 “Water quality” of the International Organization for Standardization (ISO) and has been taken over as EN ISO 17852:2008 by Technical Committee CEN/TC 230 “Water analysis“, the secretariat of which is held by DIN.
13、 This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by July 2008, and conflicting national standards shall be withdrawn at the latest by July 2008. Attention is drawn to the possibility that some of the
14、 elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document supersedes EN 13506:2001. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the follo
15、wing countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slov
16、enia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 17852:2006 has been approved by CEN as EN ISO 17852:2008 without any modifications. BS EN ISO 17852:2008iiiContents Page1 Scope 12 Normative references 13 Principle 24 Interferences 25 Reagents and standards
17、. 26 Apparatus and instrumentation . 57 Sample collection and pre-treatment . 68 Instrumental set up 69 Procedure . 710 Test report 811 Precision . 8Annex A (informative) Additional information . 9Annex B (informative) Schematic block diagram 10Annex C (informative) Availability of reagents 11Annex
18、D (informative) Precision data . 12Bibliography . 13BS EN ISO 17852:2008blankvIntroductionIn natural water sources, mercury compounds generally occur in very small concentrations of less than .Higher concentrations may be found, for example, in industrial waste water.Both inorganic and organic compo
19、unds of mercury may be present. Mercury can also accumulate in sedimentand sludge.In order to fully decompose all of the mercury compounds, a digestion procedure is necessary. Digestion can beomitted only if it is certain that the mercury concentration can be measured without this pre-treatment.The
20、user should be aware that particular problems could require the specification of additional marginalconditions.0,1g/lBS EN ISO 17852:2008blank1Water quality Determination of mercury Method using atomic fluorescence spectrometryWARNING Persons using this International Standard should be familiar with
21、 normal laboratorypractice. This standard does not purport to address all of the safety problems, if any, associated with itsuse. It is the responsibility of the user to establish appropriate safety and health practices and toensure compliance with any national regulatory conditions.IMPORTANT It is
22、absolutely essential that tests conducted according to this International Standardare carried out by suitably qualified staff.1ScopeThis International Standard specifies a method for the determination of mercury in drinking, surface, ground andrain water using atomic fluorescence spectrometry.NOTE T
23、his International Standard may be applied to industrial and municipal waste water after an additional digestion stepunder appropriate conditions.The potential linear dynamic range is approximately to . In practice, the working range is oftenfrom to .Samples containing mercury at concentrations highe
24、r than the working range can be analysed followingappropriate dilution of the sample.The method detection limit ( ) will be dependent on the selected operating conditions and calibration range.With high purity reagents, a of less than is obtainable.The relative standard deviation is typically less t
25、han for concentrations greater than twenty times themethod detection limit.The sensitivity of this method is dependent on the selected operating conditions.2 Normative referencesThe following referenced documents are indispensable for the application of this document. For datedreferences, only the e
26、dition cited applies. For undated references, the latest edition of the referenced document(including any amendments) applies.ISO 3696, Water for analytical laboratory use Specification and test methodsISO 5667-1, Water quality Sampling Part 1: Guidance on the design of sampling programmes andsampli
27、ng techniquesISO 5667-2, Water quality Sampling Part 2: Guidance on sampling techniquesISO 5667-3, Water quality Sampling Part 3: Guidance on the preservation and handling of water samples1 ng/l 100g/l10 ng/l 10g/lxDLxDL1 ng/l5%BS EN ISO 17852:200823PrincipleAtomic fluorescence is an emission proces
28、s in which atoms are excited by the absorption of a beam ofelectromagnetic radiation. The excited species then relax to the ground state, giving up their excess energy asphotons. Intensity of the photons is measured.An aliquot of sample is digested using chemically generated bromine and bromine chlo
29、ride (BrCl)1,2. This isknown to break down all of the commonly occurring organomercury species to mercury(II). Immediately prior toanalysis, the excess bromine is removed by ascorbic acid (see A.2).Elemental mercury vapour is generated from the digested sample by reduction with tin(II) chloride, and
30、 ispurged from solution by an argon gas carrier stream. Moisture is continually removed from the gas stream andthe mercury vapour is detected by atomic fluorescence spectrometry (AFS). The procedure is usuallyautomated by means of an autosampler and control software.4 InterferencesWith mercury there
31、 is a risk that exchange reactions, that is adsorption and desorption, will occur on the wallsof sampling and reaction vessels.Mercury vapour can diffuse through various plastics; this phenomenon needs to be taken into consideration inthe choice of tubing material. Glass or special plastics tubing,
32、e.g. FEP1)tubes, may be used. Silicone tubing,for example, is unsuitable.Suppression effects resulting from quenching of the atomic fluorescence signal may be encountered. Dissolvedgaseous species are usually removed during the digestion stage.The presence of water vapour or aerosol in the fluoresce
33、nce cell may cause suppression due to quenching.Water vapour should be removed from the carrier gas stream using a hygroscopic membrane before enteringthe detector3.Anions which complex strongly with mercury can cause suppression. These include sulfide, iodide andbromide. The potassium bromide - pot
34、assium bromate reagent (5.4) causes no suppression if it is applied asrequired.The noble metals, such as gold, silver and platinum, amalgamate with mercury vapour and, therefore, maycause suppression.Volatile organics do not cause interference with the AFS method4.5 Reagents and standardsReagents an
35、d water can contain mercury as an impurity. For high sensitivity, use ultra-pure reagents or thosewith particularly low mercury content compared to the lowest analyte concentration.5.1 Water, with a purity fulfilling the requirements for grade 1 water according to ISO 3696 for all samplepreparations
36、 and dilutions.5.2 Potassium bromate solution, .Dissolve of potassium bromate in of water (5.1). Potassium bromate can be purified, if necessary,by heating in a muffle furnace overnight at .The solution is stable for about a week.1) FEP = perfluoro(ethene-propene).c(KBrO3) = 0,0333 mol/l1,39 g 250 m
37、l250C 20CBS EN ISO 17852:200835.3 Potassium bromide solution, .Dissolve of potassium bromide in of water (5.1). Potassium bromide can be purified, if necessary,by heating in a muffle furnace overnight at .The solution is stable for about a month.5.4 Potassium bromide - potassium bromate reagent.Mix
38、equal volumes of potassium bromate (5.2) and potassium bromide solution (5.3). A total volume of will allow digestion for 100 samples.Prepare on the day of use.NOTE Pre-mixed ampoules for potassium bromate-bromide stock solution are commercially available (see C.1). Thisreagent has been found to con
39、tain negligible mercury concentrations.The pre-mixed reagent may be stable for several days up to one week. This shall be checked.5.5 L-ascorbic acid solution, .Dissolve of L-ascorbic acid in water (5.1) in a volumetric flask and make up to volume.The solution is stable for about a week.5.6 Nitric a
40、cid, .See C.2.5.7 Hydrochloric acid, (HCl), .Dilute of high purity hydrochloric acid to with water(5.1).5.8 Tin(II)chloride solution, .Add of tin(II)chloride dihydrate to of hydrochloric acid (5.7). Heat to dissolve. Dilute to withwater (5.1). To remove any traces of mercury, bubble the solution wit
41、h argon, nitrogen or air, e.g. at a flow rateof per minute for .NOTE The hydrochloric acid used to prepare this solution can be analytical grade since any mercury present will beremoved on bubbling.5.9 Reagent blank.For each , prepare a solution containing of hydrochloric acid (5.7) and of potassium
42、 bromide -potassium bromate reagent (5.4) per . Add of ascorbic acid solution (5.5) for each prepared5. It is essential that the same reagents used for sample and standard preparation are used forpreparation of the reagent blank. Treat the reagent blank like a sample.NOTE On the continuous flow syst
43、em, the reagent blank solution is run as background for automatic blank subtraction.This solution may contain trace levels of detectable amounts of mercury.5.10 Mercury standard solutions5.10.1 Mercury stock solution A, .Use a commercially available quantitative standard solution.This solution is st
44、able for at least six months.c(KBr) = 0,2 mol/l5,95 g 250 ml300C 20C200 ml(C6H8O6) = 100 g/l10 g 100 ml(HNO3) = 1,4 g/mlw(HCl) = 120 g/kg167 ml w(HCl) = 360 g/kg (HCl) = 1,19 g/ml 500 ml(SnCl2 2H2O) = 20 g/l10,0 g 150 ml 500 ml2l 15 min100 ml 15 ml 2ml100 ml 100l 10 ml(Hg) = 1 000 mg/lBS EN ISO 1785
45、2:20084Alternatively use a stock solution prepared from ultra high purity grade chemicals ( massfraction pure). Dissolve of mercury(II)chloride HgCl2in water (5.1). Add of nitric acid (5.6)and dilute to .WARNING Do not dry the inorganic salt, it is highly toxic.5.10.2 Mercury stock solution B, .Dilu
46、te of stock solution A (5.10.1) with water (5.1) to approximately . Add of potassium bromide -potassium bromate reagent (5.4) and dilute to in a borosilicate volumetric flask with water.Prepare weekly.5.10.3 Mercury stock solution C, .Dilute of stock solution B (5.10.2) to with reagent blank (5.9) i
47、n a borosilicate flask.Prepare the solution on the day of use.5.10.4 Mercury stock solution D, .Dilute of stock solution C (5.10.3) to with reagent blank (5.9) in a borosilicate flask.Prepare the solution freshly before each series of measurements.5.10.5 Calibration standards.Prepare a minimum of fi
48、ve mercury calibration standards spanning the concentration range of interest by serialdilution of the stock solution D (5.10.4). Each calibration standard shall contain of hydrochloric acid (5.7)and of potassium bromide - potassium bromate reagent (5.4) per in borosilicate volumetric flasks.Plastic
49、 flasks should not be used if they are permeable to mercury(0) vapour.Prepare on the day of use.The matrix of the reagent blank solution shall be identical to that of the standard solutions. For the concentration range from to , for example, proceed as follows.Prepare 5 calibration standards of concentrations , , , and by taking, , , and respectively of mercury stock solution D (5.10.4) and diluting accurately towith reagent blank (5.9). For the concentration range from to , for example, proceed as follows.
