Office of Ground Water and Drinking Water

December 1, 2013

MEMORANDUM

SUBJECT: Basis for Expedited Approval of Methods from ASTM International 

FROM: Glynda A. Smith, Chemist

Technical Support Center

TO: The Record

This memo documents the reviews that were conducted on new versions of methods 

issued by ASTM International. It provides the background information on why EPA is 

approving these methods using the expedited method approval process. Each method is 

discussed individually below:

ASTM International Method D 3223-12:

ASTM Method D 3223-02 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 the analysis of 

mercury in water. The following changes were made in the updated version:

 Section 1.4 has been added to specify that SI units are the standard and no other units of 

measurement are used in this method.

 The Apparatus Section (7.2) adds the allowance for use of direct reading atomic 

absorption spectrometers.

 The Reagents Section (8.3) has been amended to allow use of commercially prepared 

mercury stock standard solutions. 

 In the Sampling Section, Note 6 has been added to allow pH adjustment in the laboratory 

as long as samples are received within 14 days. This reduces the hazards of transporting 

and handling acids in the field. This modification is consistent with the sample handling 

practice recommended in EPA Method 200.8 which is also approved for determination of 

mercury in water. Section 8.3 of EPA Method 200.8 states: “Preservation may be done at 

the time of collection, however, to avoid the hazards of strong acids in the field, transport 

restrictions, and possible contamination it is recommended that the samples be returned 

to the laboratory within two weeks of collection and acid preserved upon receipt in the 

laboratory.”

 In the Procedure Section, Note 8 has been added to allow the use of block digestion

systems in place of requiring digestion of samples in a water bath.

 Add subsection 14.2.4 to the Quality Control Section recommending analysis of 

continuing calibration blank and continuing calibration verification QC samples.

ASTM Method D 3223-12 is identical to the promulgated method with respect to sample 

preparation, analytical procedure and calculation of mercury concentrations in water samples. 
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The precision and bias are unchanged. Therefore, ASTM Method 3223-12 is equally as effective 

as ASTM Method D 3223-02 for determining mercury in water.

ASTM International Method D 512-12 B

ASTM Method D 512-04 B was approved for the determination of chloride ion in 

drinking water in the expedited methods approval action that was published June 3, 2008 (73 FR 

31616). In the June 2008 action, ASTM Method D 512-04 B was compared against the 

approved version, ASTM Method D 512-89 (reapproved 1999) B, which is cited in the drinking 

water regulations at 40 CFR 143.4(b). Compare the most recent update, ASTM Method D 512-

12 B, to the approved version, noting the minor revisions associated with the expedited version. 

The changes include:

 Section 1.3 has been added to specify that SI units are the standard and no other units of 

measurement are used in the method.

 Three documents (ASTM Guide D 5810, ASTM Practice D 5847, ASTM Practice E 200) 

were added to the Reference Section.

 Section 4 (Significance and Use) has been modified to indicate that chloride ion is under 

regulation in waste water as opposed to water, in general. This is an acceptable revision, 

since chloride ion is a secondary contaminant with a federally unenforceable MCL in 

drinking water.

 Water purity was changed from Type II to Type I in Section 5.2.

 Reference to ASTM Practice E 200 was corrected in Section 18.2.

 Standard silver nitrate solution concentration in Section 18.4 has been modified to list 

molarity (mole/L) as well as normality (equivalent/L).

 Section 30 (Quality Control) was added to describe the types of QC analyses that must be 

included to verify that the test results obtained using the method are valid and accurate.

The two methods are identical in respect to sample collection/handling protocols, sample 

preparation, titration procedure and calculation of chloride ion concentration in the sample. The 

precision and bias are unchanged. Therefore, ASTM Method D 512-12 B is equally as effective 

as ASTM D 512-89 (reapproved 1999) B for determining chloride ion concentrations in water.

ASTM International Method D 4327-11

ASTM Method D4327-03 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 the analysis of 

fluoride, nitrate, nitrite, and orthophosphate in water; the method is also cited in the drinking 

water regulations at 40 CFR 143.4(b) for determining chloride and sulfate in water. The 

following changes were made in the updated version:

 In Section 1.4 of the Scope, suggestions for lowering detection limits (e.g., increase 

sample injection loop volume) have been generalized to encompass the use of newer 

instrumentation, column technology and eluents.

 Section 1.7 has been added approving the use of electrolytically generated eluents, 

electrolytically regenerated eluents, electrolytic suppression and electrolytic trap columns 

(used to purify returning eluent in electrolytically regenerated eluent systems). The basis 

for this approval are two ATP letters that are attached to ASTM Method D 4327-11. The 

letters establish method equivalency for the use of these techniques to improve reliability 

and reproducibility and reduce waste.
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 Section 1.8 has been added to specify that SI units are the standard and no other units of 

measurement are used in the method.

 Section 4.1 has been modified to include the use of electrolytic suppressors which do not 

require sulfuric acid.

 Section 5, Note 2 has been modified to suggest the option of using hydroxide based 

eluents in place of carbonate eluents if interference in the determination of the early 

eluting fluoride ion cannot be resolved.

 Section 7.1.5 has been expanded to encompass electrolytic suppressor devices.

 Section 8.3.1 has been added to describe preparation of hydroxide eluent as an alternative 

to carbonate based eluent.

 Each stock solution preparation described in Section 8.5 contains the additional option of 

using commercially available certified stock solutions instead of manual preparation.

 Section 10.1.3 clarifies that elution order in Figure 1 was obtained using carbonate based 

eluent; if hydroxide eluent is used, the elution order of sulfate and phosphate will be 

reversed.

 Section 11.2 has been expanded to discuss options for reducing background, specifically 

using hydroxide eluent because hydroxide is reduced to water in the suppressor, or using 

an additional carbonate removal device if carbonate eluent is used.

ASTM Method D 4327-11 is identical to the promulgated method with respect to sample 

collection/handling protocols, sample preparation, analytical procedure, calculation of anion 

concentrations, and required quality control procedures. The precision and bias are unchanged. 

Therefore, ASTM Method D 4327-11 is equally as effective as ASTM Method D 4327-03 for the 

determination of fluoride, nitrate, nitrite, orthophosphate, chloride and sulfate in water.