ASTM D7441-08(2013)

Standard Practice for Separation of Beryllium from Other Metals in Digestion and Extraction Solutions from Workplace Dust Samples (Withdrawn 2018)

SIGNIFICANCE AND USE
5.1 Beryllium is an important analyte in industrial hygiene because of the risk of exposed workers developing Chronic Beryllium Disease (CBD). CBD is a granulomatous lung disease that is caused by the body’s immune system response to inhaled dust or fumes containing beryllium, a human carcinogen (2). Surface wipe samples and air filter samples are collected to monitor the workplace. This practice addresses the problem of spurious results caused by the presence of interfering elements in the solution analyzed. The practice has been evaluated for all elements having emission spectra near the 313.042 and 313.107 nm beryllium lines, as well as elements of general concern including aluminum, calcium, iron and lead. Below is a table listing each possible spectrally interfering element:    
Cerium  
Chromium  
Hafnium  
Molybdenum  
Niobium  
Thorium  
Titanium  
Thulium  
Uranium  
Vanadium  
Uranium  
Measurement of beryllium on the order of 1 ppb (0.003 µg Be/100 cm2 wipe sample) has been successfully accomplished in the presence of spectrally interfering elements on the order of hundreds of ppm. This method has been validated on matrices containing 10 mg of each of the above elements. In some cases including interferents such as chromium and calcium, the single 2 mL beryllium extraction chromatography resin can handle >100 mg of total dissolved solids and still deliver >90 % beryllium yield. Should the matrix contain greater amounts of contaminants, additional resin may be used or, more likely, a combination of different resins may be used. (3,4).
SCOPE
1.1 This practice covers the separation of beryllium from other metals and metalloids in acid solutions, by extraction chromatography, for subsequent determination of beryllium by atomic spectroscopy techniques such as inductively coupled plasma atomic emission spectroscopy (ICP-AES).  
1.2 This practice is applicable to samples of settled dust that have been collected in accordance with Practices D6966 or D7296.  
1.3 This practice is compatible with a wide variety of acid digestion techniques used in digesting settled dust samples, such as those described in Test Method D7035.  
1.4 This practice is appropriate for the preparation of settled dust samples where an unacceptable bias is suspected or known because of spectral interferences caused by other metals or metalloids present in the sample. This practice may also be appropriate for the analysis of other types of samples.  
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
WITHDRAWN RATIONALE
Formerly under the jurisdiction of Committee D22 on Air Quality, this practice was withdrawn in October 2018. This standard was withdrawn without replacement due to its limited use by the industry.
This practice covers the separation of beryllium from other metals and metalloids in acid solutions, by extraction chromatography, for subsequent determination of beryllium by atomic spectroscopy techniques such as inductively coupled plasma atomic emission spectroscopy (ICP-AES).

General Information

• Status: Withdrawn
• Publication Date: 31-Mar-2013
• Withdrawal Date: 02-Oct-2018
• ICS: 13.040.20 - Ambient atmospheres
• Technical Committee: D22 - Air Quality
• Drafting Committee: D22.04 - Workplace Air Quality

Relations

• Replaces: ASTM D7441-08 - Standard Practice for Separation of Beryllium from Other Metals in Digestion and Extraction Solutions from Workplace Dust Samples
• Effective Date: 01-Apr-2013

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: D7441 − 08 (Reapproved 2013)
Standard Practice for
Separation of Beryllium from Other Metals in Digestion and
Extraction Solutions from Workplace Dust Samples
This standard is issued under the fixed designation D7441; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope alloids in Airborne Particulate Matter by Inductively
Coupled Plasma Atomic Emission Spectrometry (ICP-
1.1 This practice covers the separation of beryllium from
AES)
other metals and metalloids in acid solutions, by extraction
D7296 Practice for Collection of Settled Dust Samples
chromatography, for subsequent determination of beryllium by
Using Dry Wipe Sampling Methods for Subsequent De-
atomic spectroscopy techniques such as inductively coupled
termination of Beryllium and Compounds
plasma atomic emission spectroscopy (ICP-AES).
E882 Guide for Accountability and Quality Control in the
1.2 This practice is applicable to samples of settled dust that
Chemical Analysis Laboratory
have been collected in accordance with Practices D6966 or
D7296.
3. Terminology
1.3 This practice is compatible with a wide variety of acid
3.1 For discussion of pertinent terms not discussed here, see
digestion techniques used in digesting settled dust samples,
Terminology D1356.
such as those described in Test Method D7035.
3.2 Definitions:
1.4 This practice is appropriate for the preparation of settled
3.2.1 digestion—dissolution using a combination of acids
dustsampleswhereanunacceptablebiasissuspectedorknown
and other reagents of solid materials into solution for subse-
because of spectral interferences caused by other metals or
quent instrumental analysis.
metalloids present in the sample. This practice may also be
3.2.2 eluate—the effluent from a chromatography or resin
appropriate for the analysis of other types of samples.
column.
1.5 This standard does not purport to address all of the
3.2.3 extraction chromatography—liquid chromatography
safety concerns, if any, associated with its use. It is the
applied to the separation of metal ions utilizing selective
responsibility of the user of this standard to establish appro-
organic extractants as the stationary phase and the aqueous
priate safety and health practices and determine the applica-
solution as the mobile phase (1) .
bility of regulatory limitations prior to use.
3.2.3.1 Discussion—Extraction chromatography resins con-
sist of inert porous beads coated with selective extractants.
2. Referenced Documents
2 3.2.4 spectral interference—an interference caused by the
2.1 ASTM Standards:
emission from a species other than the analyte of interest.
D1193 Specification for Reagent Water
D7035
D1356 Terminology Relating to Sampling and Analysis of
3.2.5 surface wipe—refers either to a wetted wipe, as
Atmospheres
defined in Practice D6966, or to a dry wipe, as defined in
D6966 Practice for Collection of Settled Dust Samples
Practice D7296, used to gather material from a surface for
Using Wipe Sampling Methods for Subsequent Determi-
subsequent analysis.
nation of Metals
3.2.5.1 Discussion—The terms wipe sampling, swipe
D7035 Test Method for Determination of Metals and Met-
sampling, and smear sampling describe the techniques used to
assess surface contamination on the skin, work surfaces, and
This practice is under the jurisdiction ofASTM Committee D22 on Air Quality
PPE surfaces (for example, gloves, respirators, aprons, etc.)
and is the direct responsibility of Subcommittee D22.04 on WorkplaceAir Quality.
3.2.6 vacuum box—container used to maintain a vacuum on
Current edition approved April 1, 2013. Published April 2013. Originally
approved in 2008. Last previous edition approved in 2008 as D7441 – 08. a resin or column sample in order to increase the rate of flow
DOI:10.1520/D7441-08R13.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on The boldface numbers in parentheses refer to a list of references at the end of
the ASTM website. this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D7441 − 08 (2013)
of liquid through the column. Other vacuum sources such as an 6.1.2 2-mL cartridges of beryllium extraction chromatogra-
aspirator may be used. phy resin ,
6.1.3 Syringe barrel (or similar size reservoir),
6.1.4 Vacuum box, with fittings compatible with the
4. Summary of Practice
cartridges,
4.1 This practice is based on using extraction chromatogra-
6.1.5 Delivery pipet, 5 mL or 10 mL,
phy resin to separate beryllium ions from other metal ions in
6.2 Reagents:
extracts and digestates of surface wipe samples.
(See Note 1.)
4.2 Surface wipe samples are collected using Practice
6.2.1 DeionizedWater,Type I orType II in accordance with
D6966 or Practice D7296, and are then digested or extracted
Practice D1193,
into solution by mineral acids.
6.2.2 Nitric Acid (HNO ), concentrated, ρ~1.42 g/mL
(~70 % m/m),
4.3 The pH of the solution is adjusted to between 1 and 2
6.2.3 Boric Acid (H BO ),
3 3
with sodium acetate.
6.2.4 Ammonium Oxalate monohydrate (NH C H O),
4 2 4
6.2.5 Sodium acetate trihydrate (C H O Na· H O),
4.4 The sample is then loaded onto the extraction chroma-
2 3 2 3 2
6.2.6 Methyl Violet (indicator grade).
tography resin column, where beryllium is retained. Matrix
interferencesarerinsedfromthecolumnwith0.2Mnitricacid.
NOTE1—Purity of Reagents—Reagentgradechemicalsshallbeusedin
all tests. Unless otherwise indicated, it is intended that all reagents
4.5 Beryllium is selectively eluted from the resin with 4 M
conform to the specifications of the Committee onAnalytical Reagents of
nitric acid and is available for analysis using the spectroscopic
the American Chemical Society where such specifications are available.
techniques such as ICP-AES (See Test Method D7035). Other grades may be used, provided it is first ascertained that the reagent
is of sufficiently high purity to permit its use without lessening the
accuracy of the determination.
5. Significance and Use
6.3 Solutions:
5.1 Beryllium is an important analyte in industrial hygiene
6.3.1 3.4 M Sodium acetate + 0.2 M Ammonium oxalate +
because of the risk of exposed workers developing Chronic
(0.2 M Boric acid): To a l-L volumetric flask, add 500 mL of
Beryllium Disease (CBD). CBD is a granulomatous lung
deionized water. Add 12.37 grams of Boric acid and mix until
disease that is caused by the body’s immune system response
dissolved. Add 28.42 grams of Ammonium oxalate monohy-
to inhaled dust or fumes containing beryllium, a human
drate and mix until dissolved. Add 462.68 grams of Sodium
carcinogen (2). Surface wipe samples and air filter samples are
acetate trihydrate and mix. Fill to 1 Lwith deionized water and
collected to monitor the workplace.This practice addresses the
mix until dissolved.
problem of spurious results caused by the presence of interfer-
NOTE 2—Boric acid is added to combat the effect of HF used in
ing elements in the solution analyzed. The practice has been
digestion. If HF is not used, the Boric acid may be omitted.
evaluated for all elements having emission spectra near the
6.3.2 Ammonium Oxalate, 0.25 M: To a l-L volumetric
313.042 and 313.107 nm beryllium lines, as well as elements
flask, add 500 mL of deionized water. Add 35.53 grams of
ofgeneralconcernincludingaluminum,calcium,ironandlead.
Ammonium oxalate monohydrate and mix until dissolved. Fill
Below is a table listing each possible spectrally interfering
to 1 L with deionized water and mix until dissolved.
element:
6.3.3 Nitric Acid, 0.2 M: To a 1-Lvolumetric flask, add 200
Cerium Chromium Hafnium Molybdenum
mL of deionized water. Add 12.5 mL of concentrated (70%)
Niobium Thorium Titanium Thulium
nitric acid (trace metal grade) and mix. Fill to 1 L with
Uranium Vanadium Uranium
deionized water and mix thoroughly.
6.3.4 Nitric Acid, 4.0 M: To a 1-Lvolumetric flask, add 200
Measurement of beryllium on the order of 1 ppb (0.003 µg
2 mL of deionized water. Add 250 mL of concentrated (70 %)
Be/100 cm wipe sample) has been successfully accomplished
nitric acid (trace metal grade) and mix. Fill to 1 L with
in the presence of spectrally interfering elements on the order
deionized water and mix thoroughly.
of hundreds of ppm. This method has been validated on
6.3.5 Methyl Violet, 0.1 % solution, in deionized water: 0.1
matrices containing 10 mg of each of the above elements. In
gm Methyl Violet per 100 mL of water.
some cases including interferents such as chromium and
calcium, the single 2 mLberyllium extraction chromatography
7. Procedure
resin can handle >100 mg of total dissolved solids and still
7.1 Wipe Digest Preparation:
deliver >90 % beryllium yield. Should the matrix contain
7.1.1 Prepare resin load solution in accordance with the
greater amounts of contaminants, additional resin may be used
chemical reagents normally used to digest beryllium surface
or, more likely, a combination of different resins may be used.
wipes.
(3,4).
6. Reagents and Materials
Beryllium extraction chromatography resin cartridge: 2 mL bed volume,
50-100 micron beads, bis (2-ethylhexyl) methanediphosphonic acid sorbed onto
6.1 Equipment:
acrylic ester beads (3, 4, 5). Quality control parameters for the resin are stated in
6.1.1 50-mL polypropylene centrifuge tubes, subsection 8.6.
D7441 − 08 (2013)
NOTE 3—Example methods for sample preparation may be found in
7.2.5 Equip the vacuum box (see 6.1.4) with a 50-mL
Test Method D7035.
polypropylene centrifuge tube for each beryllium extraction
chromatography resin cartridge.
7.1.2 Transfer extract from digested filter or wipe to a 50
7.2.6 Elute the beryllium with 15 mL of 4.0 M HNO (see
mL polypropylene centrifuge tube (see 6.1.1). The volume
6.3.4) at 1 mL/min. Collect the eluate in a 50-mL polypropyl-
should be less than 20 mL at this point. If a larger volume is
enecentrifugetube.Agreatervolumeof4Mnitricacidmaybe
requiredtoadequatelydigestthesample,checkberylliumyield
usedtoincreaseberylliumyield,butwillresultinamoredilute
with a suitable matrix spike solution to verify acceptable yield,
beryllium solution.
or consider increasing the amount of resin used. The digested
7.2.7 Analyze the eluate
...