Page 1 of 4 Office of Ground Water and Drinking Water Date 02/01 /2011

MEMORANDUM

SUBJECT: Basis for Expedited Approval of ASTM and Standard Method Revisions

FROM: Glynda Smith, Chemist, Technical Support Center

TO: The Record

This memo documents the reviews conducted on new versions of methods issued by the voluntary consensus standard bodies, Standard Methods and ASTM International. It provides the background information behind why EPA is approving these methods using the expedited methods approval process. Each method is discussed individually below:

Standard Methods 3114 B

- 09 published on

- line at http://www.standardmethods.org This revision was compared to the approved version, SM 3114 B

- 97 which is c ited at 40 CFR 141.23(k)(1) for atomic absorption determination of arsenic and selenium. The revision is nearly identical to the approved version with the following modifications:

**•** The approved version identifies argon as an alternative gas for nitrogen; h owever, the method neglects to mention argon anywhere in the text. The revised version corrects this oversight.

**•** The approved version specifies six calibration concentration levels. The revised version specifies preparation of a minimum of three calibrati on standards that encompass the linear range of the instrument (approx. 1.0 to 20 μg/L As (III) and Se (IV). The EPA Manual for the Certification of Laboratories Analyzing Drinking Water, 5 th Edition , Chapter IV, Section 7.2.3 states “...a calibration cur ve covering the sample concentration range and all target analytes should be generated...the curve should be composed of three or more points.” In addition, EPA Method 200.9 (Determination of Trace Elements by Stabilized Temperature Graphite Furnace Atomic Absorption), also approved for arsenic and selenium determination, states in Section 11.4.4 “...calibration standards (Section 7.9) prepared at three or more concentrations within the usable linear dynamic range of the analyte.” Since the change in the number of calibration concentration levels described in SM 3114 B

- 09 is consistent with those required in the laboratory certification manual a nd one of the approved EPA atomic absorption methods, SM 3114 B

- 09 is considered to be equally as effective as the promulgated version, SM 3114 B

- 97.

Standard Methods 3113 B

- 04 published on

- line at http://www.s tandardmethods.org The online revision was compared to the approved version, SM 3113 B which was published in the 19 th edition of Standard Methods for the Examination of Water and Wastewater for the analysis of antimony, arsenic, barium, beryllium, cadmium , chromium, copper, lead, nickel, and selenium (as cited at 40 CFR 141.23(k)(1)) as well as aluminum, iron, manganese, and silver (as cited at 40 CFR 143.4(b)) using electrothermal atomic absorption spectroscopy. The online revision contains the following changes relative to the approved method:

**•** The revision corrects an error in the preparation of palladium nitrate (Pd(NO 3 ) 2 • H 2 O) stock solution. Pa lladium nitrate is used as an optional matrix modifier. The method describes
prepar ation of a 4000 mg/L palladium nitrate stock solution; however, the actual concentrationPage 2 of 4 obtained using the amount specified in the approved method is 3800 mg/L. The revised version corrects this error, yielding a palladium nitrate stock concentration of 4000 mg/L.

**•** One additional difference between the revised version and the approved version in the 19 t h edition of Standard Methods for the Examination of Water and Wastewater involves the frequency of preparation of fresh calibration standard solutions. The 19 t h edition indicates that standard solutions for calibration should be prepared fresh daily. The revised version states that standard solutions should be prepared every two weeks, or more often as needed, if instrument response indicates degradation of the standards. This is a less wasteful protocol and identical to the frequency of preparation of fresh calibration solutions described in another approved atomic absorption method, EPA Method 200.9 (Determination of Trace Elements by Stabilized Temperature G raphite Furnace Atomic Absorption). As a result of the method comparison and error correction, SM 3113 B

- 04 is considered to be equally as effective as the promulgated version described in the 19 th edition

.

Standard Method 6651 B published in the 21 st e dition of Standard Methods for the Examination of Water and Wastewater and Standard Method 6651 B

- 00 published on

- line at http://www.standardmethods.org Standard Method 6651 B was promulgated for the determinat ion of the regulated herbicide, glyphosate. The versions published in the 21 st edition of Standard Methods and the on

- line version are both identical to the promulgated version published in the 20 th edition and cited at 40 CFR 141.24(e)(1). Therefore, the version in the 21 st edition and the on

- line version, SM 6651 B

- 00, are considered equally as effective as the promulgated version described in the 20 th edition.

Standard Method 6640 B published in the 21 st edition of Standard Methods for the Examinati on of Water and Wastewater and Standard Method 6640 B

- 01 published on

- line at http://www.standardmethods.org EPA Method 515.4, Revision 1.0 was used as the basis for comparison because it is currently cited in t he drinking water regulations at 40 CFR 141.24(e)(1) for determination of 2,4

- D, 2,4,5

- TP (Silvex), Dinoseb, Pentachlorophenol, and Picloram. Standard Method 6640 B was developed directly from EPA Method 515.4, Revision 1.0 and thus describes the identica l sample collection/handling protocols, sample preparation and derivatization steps, chromatographic conditions (specifically, the use of a secondary confirmation column), and electron capture detection. Standard Method 6640 B and EPA Method 515.4, Revis ion 1.0 specify the same quality control requirements and the method performance data (detection levels, accuracy and precision) are identical. Therefore, Standard Method 6640 B is equally as effective as EPA Method 515.4, Revision 1.0 in determining the concentrations of 2,4

- D, 2,4,5

- TP (Silvex), Dinoseb, Pentachlorophenol, and Picloram in drinking water. The on

- line version, Standard Method 6640 B

- 01, is identical to the version published in the 21 st edition and thus is also equally as effective as EPA M ethod 515.4, Revision 1.0 in determining the concentrations of 2,4

- D, 2,4,5

- TP (Silvex), Dinoseb, Pentachlorophenol, and Picloram in drinking water.

ASTM International D 1067

- 06 B ASTM International Method D 1067

- 02 B was used as the basis for comparison because it is currently promulgated in the drinking water regulations at 40 CFR 141.23(k)(1) for determining alkalinity in water using titrimetry

. The following changes were made in the newer version:

**•** In the Reagents Section of the method, Note 5 has been added to point out that the indicators are available commercially in prepared form

**•** Re

- worded the QC sub

- section 34.1.2.3Page 3 of 4 Other than the minor editorial changes, the two methods are identical with respect to sample collection/handling protocols, sample pre paration, analytical procedures, and calculation of alkalinity, in milliequivalents per liter, in drinking water. The experimental precision and bias are unchanged. Therefore, ASTM Method D 1067

- 06 B is equally as effective as the approved method, ASTM M ethod D 1067

- 02 B, for determining alkalinity in water.

ASTM International D 6919

- 09 ASTM International Method D 6919

- 0 3 was used as the basis for comparison because it is currently promulgated in the drinking water regulations at 40 CFR 141.23(k)(1) for determining sodium, magnesium, and calcium in water using ion chromatography

. Two very minor editorial changes were made:

**•** Section 1.3 added in order to note that SI units are used for all values in the method

**•** Section 16.5 updates reference method ASTM D 2777

- 98 to ASTM D 2777

- 06 Otherwise, the two methods are identical with respect to sample collection/handling protocols, sample preparation, analytical procedures, and calculation of sodium, magnesium, and calcium concentrations, in milligrams per liter, in drinking water.

ASTM International Method D 3972

- 09 ASTM International Method D 3972

- 02 was used as the basis for comparison because it is currently approved in the National Primary Drinking Water Regulations at 40 CFR 141.25(a) for the determination

o f isotopic uranium in water using alpha spectrometry. The following changes have been made to Method D 3972

- 09 relative to the approved version, Method D 3972

- 02:

**•** Added Section 1.2 in order to note that SI units are used for all values in the method

**•** Added ASTM International Practice C 1163 (Practice for Mounting Actinides for Alpha Spectrometry Using Neodymium Fluoride) and Practice D 7282 (Practice for Set

- up, Calibration, and Quality Control of Instruments Used for Radioactivity Measurements)

**•** Interferenc e Section 6.1 added discussion regarding potential interference of man

- made Neptunium

- 237.

**•** Precautions Section 9.1 added palliative recommendation (calcium gluconate gel) in the event of skin contact with hydrofluoric acid.

**•** Section 12.4

– Electrodeposition . Added footnote discussing alternate sample mounting for alpha spectrometry.

**•** Section 12.5.1 added reference to ASTM Practice D 7282 for guidance on the setup and calibration of the instrument, and additional quality assurance measures.

**•** Section 13.1 modif ied the concentration calculation terms; the calculation, however, remains exactly the same:

o C = net count rate has been changed to R n o A a,i has been changed to AC i (activity concentration of uranium isotope in water, Bq/L)

o A t has been changed to AC t (acti vity concentration of 232 U tracer, Bq/L)

**•** The detector efficiency calculation in Section 13.2 has equation terms modified to those below; the calculation, however, remains exactly the same:

o ε = R n,s /AC s o R n,s = net counting rate of a standard source in the e nergy region of the calibrated alpha

particle emitter, cps, and

o AC s = absolute alpha

- particle emission rate of the calibrated alpha

- particle emitter, α/sPage 4 of 4 **•** In Section 13.3 calculate the fractional uranium recovery instead of the percent recovery. The calcul ation terms have been modified as discussed in the prior two bullets; however, the calculation remains the same.

**•** A discussion about minimum detectable activity has been edited out of the revised version of the method (Sect. 13.5 in ASTM Method D 3972

- 02).

**•** Sections 13.4 and 13.5 incorporate expanded counting uncertainty and total combined propagated uncertainty calc ulations. These calculations are consistent with the U.S. Nuclear Regulatory Commission, Multi

- Agency Radiological Laboratory Analytical Protocols Manual
, NUREG

- 1576 EPA 402

- B

- 04

- 001A, July 2004, (MARLAP).

**•** Section 13.6 was added to calculate the critical level concentration (L c ). This is consistent with MARLAP

**•** In Section 13.7, calculation of the a priori minimum detectable concentration (MDC) was modified to be consistent with MARLAP

**•** In Section 5.2.2 the permissible uncertainty of the yield has been lower ed from 10% to 5%

**•** Section 15.5 has been added to specify that the level of analytes found in the method blank should be less than the critical level concentration (L c )

**•** Section 15.7.1 has been added to specify calculation of the Duplicate Error Ratio (DER) as a measure of the statistical agreement between duplicate results to ensure they agree within a 99.7% confidence level. The methods are identical with respect to drinking water sample collection/handling protocols and sample preparation. ASTM Method D39 72

- 09 and the approved version, D 3972

- 02, are analytically equivalent. The calculation of isotopic uranium concentrations has been updated to capture the uncertainty determinations outlined in MARLAP; precision and bias are unchanged. As a result, Metho d D3972

- 09 is considered to be equally as effective as D 3972

- 02 for determining isotopic uranium concentrations in drinking water.