1、Designation: D 7458 08Standard Test Method forDetermination of Beryllium in Soil, Rock, Sediment, and FlyAsh Using Ammonium Bifluoride Extraction andFluorescence Detection1This standard is issued under the fixed designation D 7458; the number immediately following the designation indicates the year
2、oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method is intended for use in the determination
3、of beryllium in samples of soil, rock, sediment, and fly ash.This test method can be used for purposes such as environ-mental remediation projects where beryllium is a contaminantof concern. It is also useful for characterization of levels ofberyllium in soil at sites where beryllium is in mining or
4、manufacturing applications, and for determination of back-ground levels of beryllium in soil.1.2 This test method assumes that samples of soil, rock,sediment, or fly ash are collected using appropriate andapplicable ASTM International standard practices.1.3 This test method includes a procedure for
5、on-site ex-traction (dissolution) of beryllium in dilute ammonium bifluo-ride, followed by analysis of aliquots of the extract solutionusing a beryllium-specific fluorescent dye.1.4 No detailed operating instructions are provided becauseof differences among various makes and models of suitablefluoro
6、metric instruments. Instead, the analyst shall follow theinstructions provided by the manufacturer of the particularinstrument. This test method does not address comparativeaccuracy of different devices or the precision between instru-ments of the same make and model.1.5 The values stated in SI unit
7、s are to be regarded asstandard. No other units of measurement are included in thisstandard.1.6 All observed and calculated values shall conform to theguidelines for significant digits and rounding established inPractice D 6026.1.6.1 The procedures used to specify how data are collected/recorded, or
8、 calculated, in this standard are regarded as theindustry standard. In addition, they are representative of thesignificant digits that generally should be retained. The proce-dures used do not consider material variation, purpose forobtaining the data, special purpose studies, or any consider-ations
9、 for the users objectives; and it is common practice toincrease or reduce significant digits of reported data to becommensurate with these considerations. It is beyond the scopeof this standard to consider significant digits used in analyticalmethods for engineering design.1.7 This test method conta
10、ins notes that are explanatory andnot part of mandatory requirements of the standard.1.8 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices an
11、d determine the applica-bility of regulatory limitations prior to use. Specific hazardsassociated with performance of this test method are describedin Section 9.2. Referenced Documents2.1 ASTM Standards:2D 653 Terminology Relating to Soil, Rock, and ContainedFluidsD 1193 Specification for Reagent Wa
12、terD 3740 Practice for Minimum Requirements for AgenciesEngaged in Testing and/or Inspection of Soil and Rock asUsed in Engineering Design and ConstructionD 4840 Guide for Sample Chain-of-Custody ProceduresD 5730 Guide for Site Characterization for EnvironmentalPurposes With Emphasis on Soil, Rock,
13、the Vadose Zoneand Ground WaterD 6026 Practice for Using Significant Digits in Geotechni-cal DataD 7202 Test Method for Determination of Beryllium in theWorkplace Using Field-Based Extraction and Fluores-cence DetectionE 177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE 691 P
14、ractice for Conducting an Interlaboratory Study toDetermine the Precision of a Test MethodE 882 Guide for Accountability and Quality Control in theChemical Analysis Laboratory2.2 Other Standard:1This test method is under the jurisdiction ofASTM Committee D18 on Soil andRock and is the direct respons
15、ibility of Subcommittee D18.01 on Surface andSubsurface Characterization.Current edition approved Oct. 1, 2008. Published October 2008.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume inf
16、ormation, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.EN ISO 8655-2 Piston-Operated Volumetric PipettesPart2: Piston Pipettes33. Terminology3.1 DefinitionsFor defini
17、tions of terms not appearinghere, see Terminology D 653.4. Summary of Test Method4.1 This standard test method is used to determine theberyllium content of soil, rock, sediment, and fly ash. Samplesare collected in the field using procedures described in ASTMInternational standards (see Guide D 5730
18、 for listings ofappropriate sample collection standards). A 0.5-gram aliquot isextracted using 3 % ammonium bifluoride solution heated at90C for 40 hours. The presence of active fluoride ions (HF bydissociation of ammonium bifluoride in acidic medium) en-ables dissolution of refractory forms of bery
19、llium, includingsilicates, borosilicates, and oxides. The extraction solutionproduced from each sample is then filtered and an aliquot ofthis extract is added to a pH-adjusted detection solution whichcontains a beryllium-specific fluorescence reagent. The fluo-rescence of this final solution is then
20、 measured on a calibratedfluorometer to quantify the amount of beryllium in the sample.This standard test method is adapted from Test MethodD 7202.4.2 The limit of quantification of this test method is 0.013milligrams beryllium per kilogram of sample, based on a0.5-gram sample (1).45. Significance a
21、nd Use5.1 Exposure to beryllium can cause a potentially fataldisease, and occupational exposure limits for beryllium in airand on surfaces have been established to reduce exposure risksto potentially affected workers (2, 3). Measurement of beryl-lium in matrices such as soil, rock, sediment, and fly
22、 ash isimportant in environmental remediation projects involvingberyllium contamination (4) and for establishment of back-ground levels of beryllium at sites where anthropogenicberyllium may have been used (2). Sampling and analyticalmethods for beryllium are needed in order to meet thechallenges re
23、lating to exposure assessment and risk reduction.Sampling and analysis methods, such as the procedure de-scribed in this test method, are desired in order to facilitatemeasurements of beryllium that can be used as a basis formanagement of remediation projects and protection of humanhealth.5.2 This t
24、est method can be used for purposes such asenvironmental remediation projects where beryllium is a con-taminant of concern. It is also useful for characterization oflevels of beryllium in soil at sites where beryllium is in miningor manufacturing applications, and for determination of back-ground le
25、vels of beryllium in soil.NOTE 1The quality of the result produced by this standard isdependent on the competence of the personnel performing it, and thesuitability of the equipment and facilities used. Agencies that meet thecriteria of Practice D 3740 are generally considered capable of competentan
26、d objective testing, sampling, inspection, etc. Users of this standard arecautioned that compliance with Practice D 3740 does not in itself assurereliable results. Reliable results depend on many factors; Practice D 3740provides a means of evaluating some of those factors.6. Interferences6.1 This te
27、st method is highly specific for beryllium. Othersolvated metal ions are either bound by ethylenediaminetet-raacetic acid (EDTA) in the detection solution, or they precipi-tate out due to the high alkalinity of the detection solution. Thefluorophore used for detection is highly specific for theberyl
28、lium divalent cation (Be+2).6.2 If iron or titanium are present in high excess in thesample (typically above 7 %), the resulting measurementsolution may appear golden-yellow. In this case the solution isleft for two hours or more for the iron or titanium (or both) toprecipitate. The solution is then
29、 re-filtered using the sameprocedure as for filtering the dissolution solution (after thedissolution step), prior to fluorescence measurement.7. Apparatus7.1 Sampling EquipmentUse sampling apparatus appro-priate for the type of media being collected (for example, soil,rock, sediment, fly ash) and it
30、s location (for example, surface,subsurface, vadose zone). Guidance on selection of appropriatesampling apparatus is found in the ASTM International stan-dards referenced in Guide D 5730.7.2 Instrumentation:7.2.1 Ultraviolet/Visible (UV/Vis) Fluorometer, with irradi-ance excitation lamp or light-emi
31、tting diode (excitationl = 380 nm) and time-integrating visible detector (400700nm, lmax 475 nm).7.2.2 Laboratory Balance, capable of measuring to thenearest 0.1 mg.7.2.3 Laboratory Oven, capable of maintaining a tempera-ture of 90 6 2C.7.3 Laboratory Supplies:7.3.1 Centrifuge Tubes, plastic, 15-mL
32、(plus 50-mL, ifnecessary).7.3.2 Polypropylene Bottles, 60 to 100 mL, with screw caps.7.3.3 Syringe Filters, 0.45-m or smaller pore size filters,for example, 13 or 25-mm diameter nylon filters, in plastichousings.7.3.4 Syringes, plastic, 5-mL or 10-mL.7.3.5 Pipetters, mechanical, of assorted sizes as
33、 needed,with tolerances in accordance with EN ISO 8655-2.7.3.6 Pipet Tips, plastic, disposable, of assorted sizes asneeded, with tolerances in accordance with EN ISO 8655-2.7.3.7 Fluorescence Cuvettes, disposable, low fluorescence,10-mm path length, transparent to UV/Visible radiation.7.3.8 Labware,
34、 plastic (for example, beakers, flasks, gradu-ated cylinders, etc.), of assorted sizes as needed.7.3.9 Forceps, plastic or plastic-coated.7.3.10 Personal Protective Wear, for example, respirators,masks, gloves, lab coats, safety eyewear, etc. as needed.7.3.11 Thermometer, to at least 100C (accuracy
35、6 1C).3Available from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Floor, New York, NY 10036, http:/www.ansi.org.4The boldface numbers in parentheses refer to the list of references at the end ofthis standard.D74580827.3.12 Other general laboratory supplies as needed.8. Reagents8
36、.1 Purity of ReagentsReagent grade chemicals shall beused. Unless otherwise indicated, it is intended that all reagentsconform to the specifications of the Committee on AnalyticalReagents of the American Chemical Society where suchspecifications are available. Other grades may be used, pro-vided it
37、is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent as defined byType I of Specification D 1193 (ASTM Type I Wate
38、r: mini-mum resistance of 18 MV-cm or equivalent).8.3 Calibration Stock Solution1000 ppm beryllium indilute nitric acid.8.4 Ethylenediaminetetraacetic acid (EDTA) disodium saltdihydrate.8.5 L-lysine monohydrochloride.8.6 10-hydroxybenzohquinoline-7-sulfonate (10-HBQS).8.7 Sodium hydroxide (NaOH).8.8
39、 Extraction (or Dissolution) Solution3 % ammoniumbifluoride (NH4HF2) solution (aqueous) for dissolution ofberyllium in collected particulate matter. The solution may beprepared by dissolving 30 6 0.3 g of solid NH4HF2in water toa total volume of 1000 mL. (WarningAmmonium bifluoridewill etch glass, s
40、o it is essential that all NH4HF2solutions becontained in plastic labware.)8.9 Detection Solution63.4 M 10-hydroxybenzohquinoline-7-sulfonate (10-HBQS) (5) / 2.5 mM ethylenedi-aminetetraacetic acid (EDTA)/50.8 mM lysine monohydro-chloride (pH adjusted to 12.8 with NaOH): The aqueousdetection reagent
41、 is prepared by the addition of 12.5 mL of 2.5mM ethylenediaminetetraacetic acid (EDTA) disodium saltdihydrate and 25 mL of 107 mM L-lysine monohydrochlorideto 3 mL of 1.1 mM 10-hydroxybenzohquinoline-7-sulfonate(10-HBQS). The pH is adjusted to 12.85 with addition ofsodium hydroxide and water added
42、to a total of 50 mL.9. Hazards9.1 Ammonium bifluoride is highly corrosive, and is verytoxic when in contact with the skin. Effects to the skin,including irritation and burns, may not be felt for several hours.Avoid exposure by contact with the skin. Use suitable personalprotective equipment (includi
43、ng impermeable gloves and eyeprotection) when working with NH4HF2. See Appendix X1 forfurther pertinent safety information.10. Procedure10.1 Sampling:10.1.1 Sample CollectionCollect samples in accordancewith applicable ASTM International standards for the type ofmedia (for example, soil, rock, sedim
44、ent, fly ash) and thelocation being sampled (for example, surface, vadose zone).Refer to Guide D 5730 in selecting applicable ASTM Interna-tional standards for sample collection.10.1.2 Sample TransportIf applicable (that is, if samplesare transported to a different location prior to sample prepara-t
45、ion and analysis), follow sampling chain-of-custody proce-dures to document sample traceability. Ensure that the docu-mentation that accompanies the samples is suitable for a chainof custody to be established in accordance with Guide D 4840.10.2 Sample PreparationWear appropriate personal pro-tectio
46、n during sample preparation and analysis activities.Perform sample preparation and analysis in a clean area that iswell removed from any possible beryllium contamination.10.2.1 Digestion of Samples:10.2.1.1 Accurately weigh (to the nearest 0.1 mg) a 0.5-gram aliquot of sample into a polypropylene bo
47、ttle. Close thelid and gently tap the lid to ensure that all of the sample fallsto the bottom of the bottle. The bottle size is typically 10 to 50mL larger than the liquid to be added.NOTE 2Care should be taken to ensure that the aliquot(s) used arerepresentative of the soil, rock, sediment, or fly
48、ash from which thesamples were taken. Guidance may be found in references (6-9).10.2.1.2 Remove the lid and, using a graduated cylinder,add 50 6 0.5 mL of 3 % ammonium bifluoride (NH4HF2)extraction solution (see 8.8). Replace the lid, making sure thelid is tight.10.2.1.3 Swirl the bottle to ensure c
49、omplete wetting of thesample.10.2.1.4 Repeat steps 10.2.1.1 through 10.2.1.3 for allsamples.10.2.1.5 Place sample bottles in a laboratory oven, pre-heated to 90 6 2C, for 40 hours.NOTE 3The 40-hour heating step may be reduced by using a moreconcentrated solution (up to 10 %) of NH4HF2. After extraction usingconcentrations at or above 5 % NH4HF2, dilution with water is required tomaintain a pH of 12 or higher when mixed with the dye solution; this pHis required to achieve quantitative recovery (10). Method evaluationshould consider the sample media, par
