Page 1 of 6 Office of Ground Water and Drinking Water

December 3, 2013

MEMORANDUM

SUBJECT : Basis for Expedited Approval of Online Standard Methods

FROM : Glynda Smith, Chemist, Technical Support Center and Steve Wendelken, Chemist, Technical Support Center

TO : T he Record

In the May 2013 expedited methods approval action (78 FR 32558, May 31, 2013), 22 nd edition Standard Methods were reviewed for equivalency relative to the versions approved in the drinking water regulations. Documentation of the reviews is recorded in the memo s entitled “Smith and Wendelken 2012b” and “Best 2013” that are associated with the expedited action’s public docket (Docket ID EPA

- HQ

- OW

- 2013

- 0300). Unless noted, each of the following online versions has been compared to the 22 nd edition version; if there are no changes, the edits in the online version are identical to those noted in the 22 nd edition version and thus, the online version is equally as effective as the ap proved version as discussed in “Smith and Wendelken 2012b” and “Best 2013”

.

# Approved Method Revised/Edited

Online Version Additional Revisions?

1 2550

- 00 2550

- 10 The online version, Standard Method 2550

- 00, was used as the basis for comparison because it is currently cited in the drinking water regulations at 40 CFR 141.23(k)(1) for the determination of temperature. The version published in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater contains the following minor
tec hnical revisions that are mainly associated with eliminating the use of mercury

- filled glass thermometers to avoid breakage and release of toxic mercury into the environment:

 Adds the use of standard liquid

- in

- glass or electronic thermometers with analog o r digital readouts;

 References the quality control criteria in Section 2020;

 Adds clarification in the calculations to indicate that all units are to be reported in terms of degrees (i.e., the determination of bulb “volume” is not intended to be a liquid volume); and,

 Adds the NIST Handbook 105

- 6 for checking tolerances The methods have the same quality control requirements and method performance criteria and thus the version in the 22 nd edition version has been determined to be equally as effective as the approved online version. The online revision, Standard Method 2550

- 10, is identical to the version in the 22 nd edition. Therefore, Standard Method 2550

- 10 can be considered equally as effective as the approved method for the determination of temperature in drinking
water. 2 3113 B

- 99 3113 B

- 10 In the evaluation of the 22 nd edition methods, the 19 th edition version was used as the basis for comparison. Since that time, Standard Methods Online has re

- loaded Standard Method 3113 B

- 99 which is currently ci ted in the drinking water regulations at 40 CFR 141.23(k)(1) for the determination of antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, nickel, and selenium; and again at 40 CFR 143.4(b) for the determination of aluminum, iron,Page 2 of 6

# Approved Method Revised/Edited

Online Version Additional Revisions?

mangane se, and silver. As a newer version, Standard Method 3113 B

- 99 was used for the comparative evaluation of Standard Method 3113 B

- 10. As with the 22 nd edition evaluation, there are numerous technical edits:

 Under ¶ 3113 B.1, the following statement in the approved method has been deleted: “It <this method> is also applicable to analysis of bismuth, germanium, gold, iridium, mercury, tellurium, thallium, and vanadium, but precision and accuracy data are not yet ava ilable. “ Of these contaminants, only mercury and thallium have NPDWRs and neither specifies this method as an approved method for compliance monitoring.

 Corrects an error in the preparation of the palladium nitrate modifier. In the approved method, the reagent prep. calls for 8.89 g Pd(NO 3 ) 2 •(H 2 O) to obtain a 4000 mg Pd/L solution; that that actually yields a 3800 mg Pd/L solution. In the version under review, the reagent prep. calls for 9.34 g Pd(NO 3 ) 2 •(H 2 O) which yields the correct 4000 mg Pd/L conce ntration.

 In the Sample Pretreatment section ( ¶ 4.a.1), “Dissolved metals” has been modified to “Dissolved metals and metals where sample turbidity is < 1 NTU”. It further states that nickel (as nickel nitrate) may be deleted if palladium is co

- added duri ng analysis.

 In ¶ 4.c (Instrument Calibration), the approved method calls for standard solutions to be prepared fresh daily. In the version under review, the calibration section has been modified to “Prepare standard solutions every 2 weeks, or more frequ ently as needed if standard response indicates degradation of standard. A decrease in signal of more than 10% requires investigation and indicates the possible need for fresh standards”. This modification is in agreement with the standard solution prepar ation practice described in EPA Method 200.9, an approved graphite furnace AA method for the same contaminants.

 In the approved method, ¶ 4.c (Instrument Calibration) specifies analysis of standards in triplicate to verify method precision. In the version under review, this has been modified to analysis of standards in duplicate. This modification was checked against EPA Method 200.9; EPA Method 200.9 has no specification for the analysis of multiple standards.

 The version under review adds a cautionary n ote in ¶ 4.d.2 (Method of Standard Additions) that the addition of the known concentrations must yield results that fall within the linear range of the method.

 In the Quality Control section , the version under review adds the statement: “The QC practices considered to be an integral part of each method can be found in Section 3020.” The methods overall are the same with respect to sample collection/handling protocols, sample preparation, analytical techniques, and calculation of metal concentrations in dr inking water. Therefore, Standard Method 3113 B

10 is equally as effective as the approved version, Standard Method 3113 B

- 99. 3 5910 B

- 00 5910 B

- 11 The online version, Standard Method 5910 B

- 00, was used as the basis for comparison because it is currently cited in the drinking water regulations at 40 CFR 141.131(d)(4)(ii) for the determination of ultraviolet (UV) absorption at 254 nm. The version published in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater contain s the following editorial and technical revisions that are primarily associated with incorporating more quality control into the method:Page 3 of 6

# Approved Method Revised/Edited

Online Version Additional Revisions?

 In paragraph 1.a, several sentences have been edited to eliminate the use of passive voice. For example, the
sentence “Samples are filtered to control variations in UV absorption caused by particles” has been revised to “Filter samples to control particle

- related variations in UV absorption.”

 In paragraph 1.a, the sentence “Adjustment of pH before filtration is optional” has been replaced and expanded by the sentence “The sample’s pH should be adjusted before filtration; however, certain organic constituents (e.g., humic substances) may be lost to filters, suspended particles, or vessel walls at lower pH values. When filt ering samples for SUVA determination, do not adjust pH before filtration.” These instructions relating to SUVA (specific UV absorption) determination are taken directly from the specifications in the regulations at 40 CFR 141.131(d)(4)(ii). These instruc tions are repeated in paragraphs 1.d and 4.b.

 In paragraph 1.b, “UV

- absorbing organics other than those of interest” has been added to the list of potential interferences.

 In paragraph 1.c, the statement “Dilute high

- strength samples to fall within the det ermined range” has been added. This is consistent with the QC specification defined in EPA methods that prohibits extrapolation beyond the calibrated range.

 Adds a new paragraph 1.d which details preparation of sample collection vessels, sampling, shippin g conditions, and storage of collected samples.

 In paragraph 2.b, additional optional filters are listed for removing gross particulates, such as polyether sulfone (PES) and hydrophilic polypropylene (HPP). Includes instructions for handling highly turbid samples such as would be expected in some wastewater samples.

 In paragraph 3.a, the specification for organic

- free water has been changed from “reagent water...containing less that 0.05 mg DOC/L” to “reagent water containing less than 0.010 cm

- 1 of UV

- abs orbing compounds. For optimum performance, reagent water of less than 0.0045 cm

- 1 is recommended.” Since the method is based on determination of UV absorption, it is reasonable to base the background specification on UV absorption as well, rather than a different physical parameter.

 In paragraph 4.a, there is a minor change in the suggested UV absorbance range from 0.005 to 0.900 cm

- 1 to 0.005 to 0.950 cm
- 1 for determining an appropriate sample volume. This is not a method criterion, but rather a suggest ed range.

 In paragraph 6, several additions have been made to the method Quality Control. A revision has been added that references the QC criteria in Section 5020 and instructs the analyst to also follow all QC described within the method.

 Paragraph 6.b adds the specification for duplicate analyses, determination of the relative percent difference (RPD), and RPD limits: for UV values > 0.045 cm

- 1 , the RPD limit is < 10%; for UV values < 0.045 cm

- 1 , the RPD limit is < 20%.

 Adds a new paragraph, 6.d, whic h adds the specification for including filter blanks with each batch of filtered samples.Page 4 of 6

# Approved Method Revised/Edited

Online Version Additional Revisions?

 Adds a new paragraph 6.e, which adds the option of checking filtrate turbidities if a UV value or calculated SUVA seems unusually high.

 Paragraph 6.f adds a QC check for the spectrometer by preparation and addition of at least one KHP standard in the range of interest with each analytical batch. The quality control requirements in the 22 nd edition version of this method have been considerably strengthened relative to the approved version. The updated 2011 online version , Standard Method 5910 B

- 11, contains the same editorial and technical revisions detailed for the 22 nd edition version. T herefore, Standard Method 5910 B

- 11 can be considered equally as effective as the approved method for the determination of UV absorption at 254 nm in drinking
water. 4 6251 B

- 94 6251 B

- 07 The online version, Standard Method 6251 B

- 94, was used as the basis for comparison because it is currently cited in the drinking water regulations at 40 CFR 141.131(b)(1) for the determination of HAA5 (monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid). Th e version published in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater is identical to the approved online version with the minor editorial revision that references the quality control criteria in Section 6020. Standard Me thod 6251 B

- 07 is the current online version and it is identical to the 22 nd edition version. Therefore, Standard Method 6251 B

- 07 can be considered equally as effective as the approved method for the determination of HAA5 in drinking
water. 5 EPA Method

515.4 6640 B

- 06 EPA Method 515.4, Revision 1.0 was used as the basis for comparison because it is currently cited in the drinking water regulations at 40 CFR 141.24(e)(1) for the determination of Dalapon, 2,4

- D, 2,4,5

- TP (Silvex), Dinoseb, Pentachlorophen ol, and Picloram. Standard Method 6640 B was developed directly from EPA Method 515.4, Revision 1.0 and thus de fin es identical sample collection/handling protocols, sample preparation and derivatization steps, chromatographic conditions, and electron capt ure detection. Standard Method 6640 B in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater and EPA Method 515.4, Revision 1.0 specify the same quality control requirements and have the same method performance data. Standard Method 6640 B

- 06 is the current online version and it is identical to Method 6640 B in the 22 nd edition version. Therefore, Standard Method 6640 B

- 06 can be considered equally as effective as the approved method for the determination of Dalapon, 2,4

- D, 2 ,4,5

- TP (Silvex), Dinoseb, Pentachlorophenol, and Picloram in drinking water. 6 6651 B, 20 th edition 6651 B

- 05 The version published in the 20 th edition of Standard Methods for the Examination of Water and Wastewater was used as the basis for comparison, because it is currently cited in the drinking water regulations at 40 CFR 141.24(e)(1) for the determination of glyphosate. The version published in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater is identical to the appro ved version with the minor editorial revision that references the quality control criteria in Section 6020. Standard Method 6651 B

- 05 is the current online version and it is identical to the 22 nd edition version. Therefore, Standard Method 6651 B

- 05 can be considered equally as effective as the approved method for the determination of glyphosate in drinking water. 7 9215 B, 20 th

ed. 9215 B

- 04 The version published in the 20 th edition of Standard Methods for the Examination of Water and Wastewater was used as the basis for comparison, because it is currently cited in the drinking water regulations at 40 CFR 141.74(a)(1)Page 5 of 6

# Approved Method Revised/Edited

Online Version Additional Revisions?

for the determination of heterotrophic bacteria. The version of this method published in the 22 nd edition of Standard Methods fo r the Examination of Water and Wastewater is similar to the approved version with some minor editorial revisions that do not impact the effectiveness of the method. The online version, 9215 B

- 04, is identical to the 22 nd edition version. Therefore, Stand ard Method 9215 B

- 04 can be considered equally as effective as the approved method for the determination of heterotrophic bacteria. 8 9221 A , 20 th

ed. 9221 A

- 06 The version published in the 20 th edition of Standard Methods for the Examination of Water and Wastewater was used as the basis for comparison, because it is cited in the drinking water regulations at 40 CFR 141.21(f)(3) and at 40 CFR 141.74(a)(1) for the determination of total coliform bacteria. The version of th is method published in the 22 nd ed ition of Standard Methods for the Examination of Water and Wastewater is similar to the approved version with some minor editorial revisions that do not impact the effectiveness of the method. The online version, 9221 A

- 06, is identical to the 22 nd editio n version. Therefore, Standard Method 9221 A

- 06 can be considered equally as effective as the approved method for the determination of total coliform bacteria. 9 9221 B , 20 th

ed. 9221 B

- 06 The version published in the 20 th edition of Standard Methods for the Examination of Water and Wastewater w as used as the basis for comparison, because it is cited in the drinking water regulations at 40 CFR 141.21(f)(3), 40 CFR 141.74(a)(1)
, and more specifically, SM 9221 B.1, B.2 is cited at 40 CFR 141.852(a)(5) for the determination of total coliform bacteria. The version of th i s method published in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater is similar to the approved version with some minor editorial r evisions that do not impact the effectiveness of the method. The online version, 9221 B

- 06, is identical to the 22 nd edition version. Therefore, Standard Method 9221 B

- 06 can be considered equally as effective as the approved method for the determination of total coliform bacteria. 10 9221 C, 20 th

ed. 9221 C

- 06 The version published in the 20 th edition of Standard Methods for the Examination of Water and Wastewater was used as the basis for comparison, because it is cited in the drinking water regulation s at 40 CFR 141.74(a)(1)for the estimation of total and fecal coliform bacteria density. The version published in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater has editorial revisions along with modified Most Probable Nu mber (MPN) tables which were developed with improved statistical approaches. The changes to the version of the method published in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater do not impact the effectiveness of the met hod. The online version, 9221 C

- 06, is identical to the 22 nd edition version. Therefore, Standard Method 9221 C

- 06 can be considered equally as effective as the approved method for the estimation of total and fecal coliform bacteria density. 11 9221 E, 20 th

ed. 9221 E

- 06 The version published in the 20 th edition of Standard Methods for the Examination of Water and Wastewater was used as the basis for comparison, because it is cited in the drinking water regulations at 40 CFR 141.21(f)(5) and 40 CFR 141.74(a)(1) for the determination of fecal coliform bacteria . The version of this method published in the 22 nd edition of Stan dard Methods for the Examination of Water and Wastewater is similar to the approved version with some minor editorial revisions that do not impact the effectiveness of the method. The online version, 9221 E

- 06 is identical to the 22 nd edition version. Th erefore, Standard Method 9221 E

- 06 can be considered equally as effective as the approved method for the determination of fecal coliform bacteria.Page 6 of 6

# Approved Method Revised/Edited

Online Version Additional Revisions?

12 9221 F, 20 th

ed. 9221 F

- 06 The version published in the 20th edition of Standard Methods for the Examination of Water and Wastewater was used as the basis for comparison because it is cited in the drinking water regulations at 40 CFR 141.402(c)(2) and, more specifically, 9221 F.1 is cited at 40 CFR 141.852(a)(5) for the determination of Escherichia co li . The version of this method published in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater is similar to the approved version with some minor editorial revisions that do not impact the effectiveness of the method. The onl ine version, 9221 F

- 06 is identical to the 22 nd edition version. Therefore, Standard Method 9221 F

- 06 can be considered equally as effective as the approved method for the determination of Escherichia coli

. 13 9222 D, 20 th

ed. 9222 D

- 06 The version publi shed in the 20 th edition of Standard Methods for the Examination of Water and Wastewater was used as the basis for comparison, because it is cited in the drinking water regulations at 40 CFR 141.74(a)(1) for the determination of fecal coliform bacteria. Th e version of this method published in the 22 nd edition of Standard Methods for the Examination of Water and Wastewater is similar to the approved version with some minor editorial revisions that do not impact the effectiveness of the method. The online version, 9222 D

- 06 is identical to the 22 nd edition version. Therefore, Standard Method 9222 D

- 06 can be considered equally as effective as the approved method for the determination of fecal coliform bacteria. 14 9223 B, 20 th

ed. 9223 B

- 04 The version pu blished in the 20 th edition of Standard Methods for the Examination of Water and Wastewater was used as the basis for comparison, because it is cited in the drinking water regulations at 40 CFR 141.21(f)(3), 40 CFR 141.852(a)(5), 40 CFR 141.74(a)(1) for t he determination of total coliform bacteria, and at 40 CFR 141.402(c)(2) and at 40 CFR 141.852(a)(5) for the determination of Escherichia coli . The version of this method published in the 22 nd edition of Standard Methods for the Examination of Water and W astewater is similar to the approved version with some minor editorial revisions that do not impact the effectiveness of the method. The online version, 9223 B

- 04 is identical to the 22 nd edition version. Therefore, Standard Method 9223 B

- 04 can be consi dered equally as effective as the approved method for the determination of total coliform bacteria and Escherichia coli

.