**Page 1 PUBLIC COMMENT SUMMARIES AND RESPONSES** 

**UPDATE V TO SW-846 "TEST METHODS FOR EVALUATING SOLID WASTE,** 

**PHYSICAL/CHEMICAL METHODS"**

**July 2014**

**Prepared by:**

**TechLaw, Inc. 14500 Avion Parkway** 

**Suite 300 Chantilly, VA 20151** 

**Prepared For:**

**U.S. Environmental Protection Agency Methods Team, Office of Resource Conservation and R**  **ecovery (ORCR)**

**EPA Contract No.: GS-10F-0168J**

**EPA Work Assignment Mangers: K. Kirkland and S. Yang** 

**EPA Project Officer:**

**S. Fowler Page 2**  TABLE OF CONTENTS

**INTRODUCTION ......................................**

**................................................... .............................. 3** 

**CHAPTER ONE .......................................**

**................................................... ............................... 4** 

**CHAPTER TWO .......................................**

**................................................... .............................12** 

**CHAPTER THREE .....................................**

**................................................... ............................16** 

**CHAPTER FOUR ......................................**

**................................................... .............................18** 

**CHAPTER NINE ......................................**

**................................................... ..............................21** 

**METHOD 3200 .......................................**

**................................................... ...............................22** 

**METHOD 6010D ......................................**

**................................................... ..............................23** 

**METHOD 6020B ......................................**

**................................................... ..............................27** 

**METHOD 8000D ......................................**

**................................................... ..............................31** 

**METHOD 8021B ......................................**

**................................................... ..............................38** 

**METHOD 8111 .......................................**

**................................................... ...............................39** 

**METHOD 8270D ......................................**

**................................................... ..............................40** 

**METHOD 8290 .......................................**

**................................................... ...............................41** 

**METHOD 8410 .......................................**

**................................................... ...............................42** 

**METHOD 8430 .......................................**

**................................................... ...............................43** 

**METHOD 9014 .......................................**

**................................................... ...............................44** 

**METHOD 9040 .......................................**

**................................................... ...............................45** 

**REFERENCE TABLE ...................................**

**................................................... ..........................46** 

**GENERAL COMMENTS ..................................**

**................................................... ......................47** **Page 3** INTRODUCTION

**On October 23, 2013, the U.S. EPA published a notic e to announce the availability of,**  **and to request comment on, "Update V" (Docket EPA–H Q–RCRA–2012–0072; FRL–9901–86–**  **OSWER) to the Third Edition of EPA publication SW-8 46, "Test Methods for Evaluating Solid**  **Waste, Physical/Chemical Methods". EPA welcomed th e public to submit comments on 23 new**  **and revised analytical methods. In addition, the A gency also invited comments on revisions to**  **Chapters One through Five of EPA publication SW-846 , an ORCR Policy Statement, and other**  **guidance. The Agency has received public comment o n Update V, and after consideration, is**  **placing these new and revised methods, guidance, an d chapters in the SW-846 methods**  **compendium. EPA is issuing this update as guidance**

**.**

**This document provides draft summaries and response s to the public comments**  **submitted to date regarding those parts of the Upda te V chapters and methods which were**  **open to comment. Complete copies of the comments c an be found in the docket to the notices**  **for Update V. Page 4**  CHAPTER ONE

1. Comment: **a) Commenter #4 commented, regarding Chapter One, t hat the guide does not define the**  **difference between a limit of quantitation (LOQ) an d lower level of quantitation (LLOQ).** 

**b) Commenter #4 made a second comment on LOQ, regar ding Chapter One, Glossary Page**  **ONE-21, that the LOQ should be defined as a level w ith defined precision and bias. However,**  **the glossary text for precision states that precisi on is only to be calculated at concentrations**  **above the LLOQ. Therefore, this further implies th at the LLOQ exists at a level without known**  **precision. If the LLOQ is assumed to be at the low est calibration standard, then the guidance is**  **also implying that precision cannot be calculated a t the lowest calibration standard.**  **Recommended edit: Change definition of precision to "concentration equal to or above the** 
**LLOQ".**

Response: **The Agency agrees with the commenter (comment 1a) a nd has updated Chapter One to**  **remove the reference to limit of quantitation (LOQ) . Section 1.1.4.9 of Chapter One now reads:**  **"Sensitivity is an instrument's or method's minimum concentration that can be reliably measured**  **or reported (i.e., lower limit of quantitation [LLO Q])." The glossary text for precision is changed**  **to reflect that precision can be calculated at or a bove the LLOQ. Section 1.1.4.9 was**  **renumbered due to the addition of repeatability as Section 1.1.4.8.** 

2. Comment: **Commenter #4 commented, regarding Sec. 1.1.4 of Cha pter One, that "Sensitivity" in terms of** 
**Detection Limits and Quantitation Limits is not inc luded as data quality indicator (DQI), although**  **it is discussed later. Although "sensitivity" is c losely tied to precision and bias (i.e., without hi**  **gh precision and low bias, there is no good "sensitivi**  **ty"), data quality requirements on "sensitivity" should still be included for reliably reporting ana**  **lyte presence/absence at the detection limits and analyte quantitation at the quantitation limits**  **. For environmental analyses, one needs to know the detection limit to reliably report "detect**  **ions", the limit of detection to reliably report "non-detects", and the limit of quantitation for re**  **liably reporting "quantitative results" (http://www.denix.osd.mil/edqw/upload/Final-DQ-Fact**  **-Sheet-091409.pdf). Recommended edit: Suggest that sensitivity in term of IUPAC/ACS Criti**  **cal Level, Detection Limit, and Quantitation Limit (or the DoD's equivalent Detection Limit, Lim**  **it of Detection, and Limit of Quantitation (http://www.denix.osd.mil/edqw/upload/Final-DQ-Fact**  **-Sheet-091409.pdf) be used.**

Response: **The Agency thanks the commenter for their input, bu t disagrees with the commenter that the**  **current definition of sensitivity is not adequate. A more detailed definition of sensitivity is not**  **needed in Chapter One since it is intended as gener al guidance. For a more detailed**  **discussion of the terminology (i.e., sensitivity), readers are encouraged to reference the**  **guidance documents listed in Section 1.4 of Chapter One.** 

3. Comment: **Commenter #4 commented, regarding the first sentenc e of Section 1.1.4 of Chapter One, that**  **procedures on establishing project-specific DQIs be provided or referenced. Recommended**  **edit: Add a concise paragraph or a reference for a procedure about establishing project-specific**  **DQIs (e.g., how to establish the acceptance criteri a for project-specific relative percent**  **differences (RPDs) of laboratory duplicate analyses ).** **Page 5**

Response: **The Agency thanks the commenter for their input. C hapter One is intended as general**  **guidance and does not contain detailed instructions about how each project-specific DQI is**  **established. The project team should reference the documents listed in Sec. 1.1.2.7 and follow**  **the data quality objective (DQO) process to develop their project-specific data collection plan;**  **establish DQIs using proven, defensible statistical methods; and document how these DQI limits**  **are established in the appropriate location (e.g., laboratory Quality Management Plans (QMP),**  **method standard operating procedures (SOPs), etc.).**

4. Comment: **Commenter #4 commented, regarding Section 1.1.4.4 o f Chapter One, that only data of known**  **quality (i.e., precision and bias) can be reliably compared. Recommended edit: Add a sentence** 

**to the end of the Section - "Measurement data shall be of known and documented data quality**  **(e.g., precision and bias) to ensure comparability. "** 

Response: **The Agency agrees with the commenter and has added the following sentence to the end of**  **Section 1.1.4.4: "Further, when assessing comparabi lity, data sets should be of known and**  **documented quality."**

5. Comment: **Commenter #4 commented, regarding Sec. 1.1.4.7 of C hapter One, that if "reproducibility" is**  **addressed, that "repeatability" be also addressed. "Reproducibility" addresses inter-laboratory**  **variances and "repeatability" addresses intra-labor atory variances. The two are paired and**  **should be addressed together. Recommended edit: Pl ease reference national and international**  **standard organizations such as NIST, ISO, etc. to d efine and address both "repeatability" and**  **"reproducibility" for completeness.**

Response: **The Agency agrees with the commenter and has added a discussion of repeatability to the DQIs**  **in Section 1.1.4 of Chapter One.**

6. Comment: **Commenter #4 commented, regarding Section 1.1.4.8 o f Chapter One, that "sensitivity" is the**  **slope of a calibration curve (i.e., instrument resp onses to concentration changes) and "detection**  **limit" is the intercept of a calibration curve, but they often are mistakenly used interchangeably.**  **For all environmental analyses, one needs "critical levels" to report detections with 99%**  **confidence, "detection limits" to report non-detect s with 99% confidence, and "quantitation**  **limits" to report quantitative results with known p recision and bias. Without critical levels, one**  **cannot reliably report "presence" at or above the " critical levels". Without "detection limits", one**  **cannot reliably report "absence" at or below the "d etection limit". Therefore, one must consider**  **the sensitivity or detection limits of any chemical analyses before the sample analysis.** 

**Recommended edit: Better definition of detection an d quantitation limits needed.** 

Response: **The Agency thanks the commenter for their input. A more detailed definition of sensitivity is not**  **needed in Chapter One since it is intended as gener al guidance. For a more detailed**  **discussion of these terms, readers are encouraged t o reference the guidance documents listed**  **in Sec. 1.4 of Chapter One. Page 6** 

7. Comment: **Commenter #4 commented, regarding Sections 1.1.1, 1 .1.2, 1.1.3, 1.1.4, and 1.3.1 of Chapter**  **One, that the systematic planning process (1.1.1), DQOs (1.1.2), QAPP (1.1.3), DQIs (1.1.4),**  **and data verification and validation (1.3.1) do not provide any information on how LLOQ** 

**information should be considered. The documents re ferenced for these areas speak to method**  **detection limits (MDLs) and reporting limits (RLs). Recommended edit: Discuss how LLOQ** 

**information should be considered.**

Response: **The Agency thanks the commenter for their input, bu t disagrees with the commenter. Chapter**  **One is intended as general guidance. It is recomme nded to establish the LLOQ as the lowest**  **point of quantitation, which, in most cases, is the concentration of the lowest calibration**  **standard in the calibration curve that has been adj usted for the preparation mass and/or** 
**volume. This makes the consideration of the LLOQ l evel functionally equivalent to the RL for** 

**the individual method. Results at or above the LLO Q are quantifiable within an acceptable**  **precision and bias. Thus, the LLOQ approach suits the needs of the Resources Conservation**  **and Recovery Act (RCRA) program, because it provide s reliable and defensible results,**  **especially at the LLOQ, and can be reported with a known level of confidence for the complex**  **matrices being evaluated. The LLOQ should be estab lished at a level equal to or below the**  **regulatory limit or threshold, depending on the pro ject needs/data use.** 

8. Comment: **Commenter #4 commented, regarding Sections 1.1.4, 1 .1.4.2, and 1.1.4.6 of Chapter One, that**  **"accuracy" is a combination of "precision" and "bia s". Where "accuracy" is used in SW-846, it**  **should often be changed to "bias". Or, the term of "trueness", which is adopted as a parallel**  **term to "precision" by ISO, may be used. Also, ple ase notice that the DQIs defined in Section** 
**1.1.4 are not consistent with the DQIs defined in t he Glossary on Page ONE-17. Updated**  **guidance from EPA Quality has already changed "accu racy" to "bias". Recommended edit:**  **Suggest that "accuracy" in Section 1.1.4 be changed to "accuracy (bias)" and explain that the**  **"accuracy" originally used as PARCC was a mistake o f "bias". Also, replace Section 1.1.4.2**  **with Section 1.1.4.6 and change the title to "Accur acy (Bias)". In addition, most "accuracy" used**  **in SW-846 Update V chapters and methods should be r eplaced with "bias".** 

Response: **For consistency with the text of 1.1.4, reproducibi lity has been added to the DQI glossary**  **definition. The definition was listed as: "Reprodu cibility is defined as the closeness of the**  **agreement between the results of measurements of th e same analyte carried out under variable** 

**conditions of measurement."**

**On the other items raised in the comment, the Agenc y thanks the commenter for their input, but**  **disagrees with the commenter that the current defin itions are not adequate. More detailed** 

**definitions and discussion of these terms are not i n Chapter One since it is intended as general**  **guidance. For more detailed discussion of terms, r eaders are encouraged to reference the**  **guidance documents listed in Section 1.4 of Chapter One.** 

9. Comment: **Commenter #4 commented, regarding Chapter One, Glos sary, Page ONE-20, that the glossary**  **stipulates that: "Individual methods may recommend procedures for verifying the LLOQ and**  **acceptance limits for use until the laboratory has sufficient data to determine acceptance limits**  **statistically". However, there is no guidance on h ow to perform the statistical determination of** **Page 7**

**the LLOQ. Recommended edit: Add guidance on how to perform the statistical determination of** 
**the LLOQ.**

Response: **The Agency thanks the commenter for their input, bu t disagrees with the commenter that the**  **current definition of LLOQ is not adequate. The Gl ossary (in Chapter One) is not intended to**  **provide a procedure for statistically determining t he LLOQ. The statement quoted in Comment**  **9 is changed to read: "Individual methods may recom mend procedures for verifying the LLOQ**  **and acceptance limits for use until the laboratory has sufficient data to determine acceptance** 

**limits".**

10. Comment: **Commenter #4 commented, regarding Chapter One, Glos sary Page ONE-17, that under**  **BLANK, "Reagent blank" is improperly defined as th e same as "method blank". "Reagent**  **blank", which is mentioned in the instrument detect ion limit (IDL) addressed on Page ONE-19, is**  **assumed to be equivalent to a "method blank" that g oes through the sample preparation**  **process. This imposes a problem to the determinati on of IDL, which is based on the results of**  **multiple "reagent blanks". "Reagent blank" should be individual or a combination of individual**  **reagents that do not go through sample preparation procedures like the "method blank", and**  **hence used for IDL determination. (A method blank that goes through all sample preparation**  **procedures is used for MDL determination.) A reage nt blank is used to ensure contaminant-free**  **individual reagents are used. Only clean reagents shall be used to prepare "instrument blank"** 

**to test instrument cleanliness and "method blank" t o test the analytical systems. Recommended**  **edit: Add "reagent blank" to the "BLANK" and revise "reagent blank" definition to distinguish it**  **from "method blank" in the Glossary.**

Response: **The Agency agrees with the commenter and has added a separate definition for reagent blank**  **in addition to method blank. The following definit ion was added to Chapter One Glossary:** 

**REAGENT BLANK: Reagent blanks are analyzed to asses s background interference or**  **contamination that exists in the analytical system that might lead to**  **the reporting of elevated concentration levels or f alse positive data.**  **The reagent blank is defined as an interference-fre e blank matrix, to**  **which all reagents are added in the same volumes or proportions as**  **used in sample preparation but are NOT carried thro ugh the complete**  **sample preparation, cleanup, and determinative proc edures. The**  **purpose of a reagent blank is to gauge contaminatio n from chemical**  **inputs and instrumental factors only. A reagent bl ank is NOT run as**  **part of a digestion or preparation method.**

11. Comment: **Commenter #4 commented, regarding Chapter One, Glos sary Page ONE-18, that under FIELD**  **BLANK, there are two editorial errors in the second paragraph of FIELD BLANK. The second**  **paragraph needs revisions for clarification too. R ecommended edit: Change the second**  **paragraph to, "A field blank may also be defined as a container of reagent water or a solid blank**  **material that is opened in the field for a predefin ed period of time and then sent to the laboratory**  **for analysis. This type of field blank is typicall y used to measure ambient contamination of**  **volatile organic samples in the field." Page 8** 

Response: **The Agency agrees with the commenter. The text was revised as follows: "Field blanks may**  **also be obtained by the sampling organization to me asure ambient contamination in the field. If**  **this type of field blank is requested, a container of reagent water or a solid blank material is**  **opened in the field for a predefined period of time . The sample is then sent to the laboratory for**  **analysis."**

12. Comment: **Commenter #4 commented, regarding Chapter One, Glos sary Page ONE-19 and Chapter 3,**  **DEFINITIONS, Page THREE-2, that under IDL, the "rea gent blank" used for IDL determination**  **shall not be equivalent to the "method blank" that goes through all sample preparation**  **procedures. Recommended edit: Change the definitio n of "reagent blank" to a mixture of all**  **analytical regents of the same proportions used for sample preparation but the “reagent blank”**  **does not go through the sample preparation process. It may be used for determining IDLs**  **and/or to test the cleanliness of reagents.**

Response: **The Agency agrees with the commenter. Please see r esponse to Comment #10 above for** 

**further details.**

13. Comment: **Commenter #4 commented, regarding Chapter One, Glos sary Page ONE-20, that under**  **LABORATORY DUPLICATE that the SW-846 distinguish an d clarify "analytical" and** 

**"measurement" in the second sentence. "Measurement " should be defined as a combination of**  **"field sampling" and "laboratory analysis" and "ana lytical (analysis)" be defined a combination of**  **"sample preparation" and "instrument determination" . (See Section 2.2.4 of SW-846 Chapter**  **Two) Recommended edit: Delete the "or measurement" from the second sentence.** 

Response: **The Agency thanks the commenter for their input, bu t disagrees that a change is needed in this** 

**section.**

14. Comment: **Commenter #4 commented, regarding Chapter One, Glos sary Page ONE-20, that under LLOQ,** 
**the introduction of LLOQ is not clear. A LOQ is we ll and commonly defined as "the minimum**  **levels, concentrations, or quantities of a target v ariable (e.g., target analyte) that can be**  **reported with a specified degree of confidence". A n LLOQ could be established at the lowest**  **calibration standard if the precision and bias at t he lowest calibration standard are established**  **and documented. Recommended edit: Suggest that LLO Q be changed to LOQ to comply with**  **well accepted national and international definition for LOQ, and provide procedures or guidance**  **for establishing laboratory-specific LOQ.**

Response: **The Agency thanks for commenter for their input. T he reference to LOQ has been removed**  **from Chapter One. Page 9** 

15. Comment: **Commenter #4 commented, regarding Chapter One, Glos sary Page ONE-21, that under**  **METHOD BLANK, the acceptance criteria for method bl ank should be "less than or equal to**  **50% of the LLOQ (except for common laboratory blank contaminants which shall be less than or**  **equal to the LLOQ), 10% of the amount measured in a ny associated batch samples, or 10% of**  **the regulatory limit, whichever is greater. If dat a uncertainty of method blank results, decision**  **errors, and practical issues are considered, method blanks should be less than or equal to 50%**  **of the LLOQ (or LOQ for common laboratory contamina nts) and 10% of sample concentrations**  **or regulatory limits, whichever is greater." Recom mended edit: Change the second to the last** 

**sentence to "The method blank results should not be greater than 50% of the LLOQ (or the**  **LLOQ for common laboratory contaminants), 10% of th e amount measured in any associated**  **batch samples, or 10% of the regulatory limit, whic hever is greater."** 

Response: **The Agency thanks the commenter for their input. C hapter One is intended as general**  **guidance; as such it does not discuss method blank acceptance criteria for individual**  **procedures. The reader should look to the individu al determinative methods for that** 

**information.**

16. Comment: **Commenter #4 commented, regarding Chapter One, Glos sary Page ONE-21, that under**  **PRECISION, the numerator for the RPD should include an absolute sign (i.e., RPD = (100) |(X1**  **- X2)| / [(X1 + X2) / 2]). Duplicate/replicate sho uld be independently prepared and analyzed,**  **and the text needs to clarify the "independently" p repared and analyzed. Duplicate or replicate**  **samples should be "independently" prepared and anal yzed, but in practice it is typically not**  **"independently" prepared and analyzed. Recommended edit: Change the RPD equation to**  **RPD = (100) |(X1 - X2)| / [(X1 + X2) / 2]. Change the last sentence to "independently prepared**  **and analyzed" and clarify "independently".**

Response: **The Agency agrees with the commenter and has modifi ed the language and the equation for**  **RPD in Chapter One to: "The agreement among a set o f replicate measurements without**  **assumption of knowledge of the true value. Precisi on is estimated by means of**  **duplicate/replicate analyses of separate aliquots o f the same sample (not multiple runs of a**  **single digestion/extraction). These samples should contain concentrations of analyte at or**  **above the LLOQ, and may involve the use of matrix s pikes. The most commonly used**  **estimates of precision are:"**

 = |   −  |

  + 

2 ∗ 	100

17. Comment: **Commenter #4 commented, regarding Chapter One, Glos sary Page ONE-22, that under**  **QUALITY CONTROL SAMPLE, "Analytical batch" is not c learly defined. An analytical batch is**  **composed of a "sample preparation batch" and an "in strument determination batch". Based on**  **the example QC samples addressed in the paragraph, the batch should be a "sample**  **preparation batch". The QC samples for an "instrum ent determination batch" include calibration**  **blanks, calibration verifications, post digestion s pike, etc. Recommended edit: Change the "an**  **analytical batch" to "a sample preparation batch". Page 10** 

Response: **The Agency agrees with the commenter and has modifi ed the glossary for "QUALITY**  **CONTROL SAMPLE" in Chapter One to read: "A sample m ade from standards or matrix and**  **used to verify acceptability of the results from pr eparation and/or analysis of a batch of samples.**  **Examples of laboratory quality control samples are method blanks, laboratory duplicates, and**  **laboratory control samples; field quality control s amples are field blanks, trip blanks, field**  **duplicates, and matrix spikes."**

18. Comment: **Commenter #4 recommended, regarding Chapter One, Gl ossary Page ONE-23, that under**  **REPRESENTATIVENESS, delete "and precisely" from the first sentence. Accuracy is a**  **combination of high precision and low bias. Hence, "accurately" covers "precisely".**  **Recommended edit: Delete "and precisely" from the first sentence.** 

Response: **The Agency agrees with the commenter and has made t he requested edit in the text.** 

19. Comment: **Commenter #4 recommended, regarding Chapter One, Gl ossary Page ONE-23, that the third**  **and fourth sentences be revised for consistency. R ecommended edit: Change the third and**  **fourth sentences to "Surrogate spikes are added to field samples and QC samples for organic**  **analyses at known amounts and their recoveries are used to assess matrix effects and, to some**  **extent, verify proper processing and instrument per formance for each sample. The analytes**  **used as surrogates mimic the behavior of the target analyte(s) throughout sample preparation** 

**and instrument determination."**

Response: **The Agency agrees with the commenter and has made t he suggested edits to Chapter One.** 

20. Comment: **Commenter #9 commented, regarding Chapter One and C hapter Nine, that additional guidance**  **has been provided in the proposed revision of Chapt er One (including references) regarding the**  **calculation of the upper confidence limit (UCL) for making the determination as to whether a**  **waste may be hazardous. Specifically, in Section 1 .1.3.2 of Chapter One, several documents**  **are listed for the development of Sampling and Anal ysis Plans. At least two of these documents** 

**contradict one another in their use of the UCL for making the determination that the analytical**  **results for a given waste could exceed the RCRA lim it.** 

**• In SW-846, Chapter 9, page 16, starting in Sectio n 7 and Equation 6 (which is repeated**  **multiple times in Chapter 9), the two-tailed critic al value for the Student's t distribution is used.** 

**• In Chapter One, Reference 8, "RCRA Waste Sampling Draft Technical Guidance" (EPA 503-**  **D-02-002), in Section 3.4.3.1, Appendices F (Equati on F.6) and G (Table G-1) the single-tailed** 

**critical value for the Student's t distribution is used.** 

**The commenter believes that use of the single-taile d critical value is statistically correct and**  **asks that either Chapter Nine be revised to utilize the single-tailed critical value for the UCL or**  **the conflicting references in Chapter One be remove d.** **Page 11**

Response: **Chapter One does not directly discuss the Student t test referred to by the commenter. The**  **Commenter is comparing a discussion of the two-tail ed Student’s t found in Chapter 9 with a** 

**different version of Student’s t test found in one of the references provided in Chapter One.**  **Chapter One expresses no preference between the two differing methods of statistical analysis,**  **but merely lists additional references that can be used to find more detailed discussions on**  **various topics. Chapter One is intended to be gene ral guidance and cannot discuss in detail**  **every specific scenario and/or conflict (if they ex ist) between reference documents.** 

**In addition, Chapter Nine is not included in Update V and as such, is not subject to revision at**  **this time. The Agency thanks the commenter for the ir input and the comment will be discussed**  **the next time Chapter Nine is updated. Page 12**  CHAPTER TWO

1. Comment: **Commenter #1 commented, regarding Chapter Two, that another document in the Docket,**  **specifically EPA-HQ-RCRA-2012-0072-0019, needs revi sions to its Figure 2-2 (entitled**  **"Schematic of Sequence to Determine if a Waste is H azardous by Characteristic") as follows:**  **A. The figure's references to "49 CFR 173.300" and "49 CFR 173.151" make it clear that the**  **schematic does not reflect the extensive changes ma de by EPA to 261.21 in the July 14, 2006**  **Federal Register. B. The diamond reading "Is waste a gas" should be c**  **hanged to "Is waste a containerized gas" to reflect EPA's position as stated in RO# 14823 th**  **at non-containerized gases are not solid**

**waste. C. The box "Perform Paint Filter Test (method 9095)**  **" should have the left arrow leaving that box changed from "Liquid" to "Liquid Result" and the ri**  **ght arrow changed from "Solid" to "Solid Result." This will prevent a reader from erroneous**  **ly concluding that no solids can be present for the "liquids" direction or that no liquids can be p**  **resent for the "solids" direction.**

**D. The diamond "Is total concentration of TC consti tuents ÷ 20 < TC regulatory limit?" should be**  **changed to reflect the formula given in RO# 14695 a nd the Dec 21, 1995 FR (on page 66389),**  **since the 20:1 ratio will decrease to 1:1 as the pe rcentage of solids present decreases from**  **100% to 0%. Also note that the procedure used for determining that percentage is not the**  **above-mentioned 9095 paint filter test but instead the 50 psi filtering procedure found within the**  **1311 TCLP test. This latter procedure will remove much more liquid from a sample than the**  **9095 procedure will. E. The schematic does not give a proper determinati**  **on for a gel that has a pH of 2 or below (or 12.5 or above). Specifically, if a gel does not pr**  **oduce a liquid result with the 9095 Paint Filter Test, it is nonetheless a D002 if a pH reading can**  **be obtained that is at or below 2 (or at or above 12.5). This is made clear in RO# 11719 (whic**  **h is identified in RCRA online as "Official OSW Policy"). Yet the schematic never shows such a**  **gel as needing to be checked for corrosivity. (Note that 261.22(a) (1) requires a w**  **aste to be aqueous, not that it be a liquid; gels can be aqueous while at the same time not necessari**  **ly liquids [particularly when 9095 is the measure of whether a waste is a liquid].)** 

Response: **The Agency thanks the commenter for their input. T he responses to this comment are labeled**  **A through E, as the individual comments had varying resolutions:** 

**Comment 1A: Regarding the CFR listing in comment 1A , the Agency agrees with the** 

**commenter and has removed the outdated references.**

**Comment 1B: The Agency agrees with the commenter an d has changed the description to “is**  **the waste a containerized gas?” as requested.**

**Comment 1C: The Agency disagrees with the commenter and no change was made to the paint** 

**filter section.**

**Comment 1D: The Agency agrees with the commenter an d acknowledges that biphasic or**  **multiphasic wastes pose an additional challenge for the user. The diagram has been updated**  **and a reference to the Federal Register (Dec 21, 19 95 page 66389) has been added.**  **http://nepis.epa.gov/Exe/ZyNET.exe/10001E3Y.txt?ZyA ctionD=ZyDocument&Client=EPA&Inde**  **x=1995%20Thru%201999&Docs=&Query=&Time=&EndTime=&Se archMethod=1&TocRestrict=** **Page 13**

**n&Toc=&TocEntry=&QField=&QFieldYear=&QFieldMonth=&Q FieldDay=&UseQField=&IntQFiel**  **dOp=0&ExtQFieldOp=0&XmlQuery=&File=D%3A\ZYFILES\IND EX%20DATA\95THRU99\TXT\**  **00000000\10001E3Y.txt&User=ANONYMOUS&Password=anony mous&SortMethod=h|-**  **&MaximumDocuments=1&FuzzyDegree=0&ImageQuality=r75g 8/r75g8/x150y150g16/i425&Dis**  **play=p|f&DefSeekPage=x&SearchBack=ZyActionL&Back=Zy ActionS&BackDesc=Results%20p**  **age&MaximumPages=1&ZyEntry=48**

**Comment 1E: A footnote has been added showing where the reader can find RO#11719, which**  **discusses gels. Gels present unique problems to cha racterization, as they can be aqueous, but**  **still pass a paint filter test. Care should be tak en when performing corrosivity measurement in a**  **gel matrix as the gels can block the ceramic juncti ons in some types of pH probes.**  **http://yosemite.epa.gov/osw/rcra.nsf/0/7D573EA3E0F1 576D8525670F006BEA5F/$file/11719.p** 

**df**

2. Comment: **Commenter #4 commented, regarding Chapter Two, Page 84, number 8, that there is an extra**  **"." Recommended edit: Correct Typo.**

Response: **The Agency agrees with the commenter. The publishe d PDF shows an extra period (in number**  **8 of Appendix A on Page 84) that was not present in the source document. The typo was** 

**corrected in the final version.**

3. Comment **Commenter #4 commented, regarding Chapter Two, Sect ion 2.3.3, Page 10, that this Section is**  **incomplete. Missing are methods 8520, 8540, and 83 25. Recommended edit: Add methods**  **8520, 8540, and 8325 to this Section.**

Response: **The Agency agrees with the commenter. The methods were added to Section 2.3.3 and the**  **following tables were added and/or modified as requ ired: Method 8520 (Table 2-36A), Method**  **8325 (Table 2-30) and Method 8540 (Table 2-30).**

4. Comment: **Commenter #4 asked, regarding Chapter Two, Section 2.3.3, Page 10, 4th and 5th paragraphs,**  **"Why does the discussion of Methods 8260 and 8270 c larify they employ capillary columns**  **when the discussion of Methods 8081, 8082, 8141, an d 8151 does not? This omission implies**  **they do not use capillary columns. This same comme nt is true of Method 8410 (stated as**  **capillary gas chromatography (GC) using Fourier Tra nsform infrared (FT-IR)) and Method 8430**  **(which is stated as GC using FT-IR but does not men tion that it is also a capillary column**  **method)." Recommended edit: Clarify the use of cap illary columns in methods 8081, 8082,**  **8141, 8151, 8410, and 8430.**

Response: **The Agency acknowledges the commenter's observation that an unintended distinction was**  **made here. The word capillary was removed as all G C and GC/mass spectrometer (MS)**  **methods now employ capillary columns. The use of o lder technologies (such as the packed** 

**columns that used to be an alternative to the moder n capillary) is not encouraged. The**  **reference to "capillary" GC methods was removed in Section 2.3.3 of Chapter 2.** **Page 14**

5. Comment: **Commenter #4 recommended, regarding Chapter Two, Se ction 2.3.3, Page 10, second to last**  **paragraph, that Method 8321 should not be included. All other methods in this Section are high**  **performance liquid chromatography (HPLC) as stated in the first sentence, but this method is** 

**HPLC/MS. Recommended edit: Delete Method 8321 from this Section.** 

Response: **The Agency thanks the commenter for their input, bu t disagrees. Method 8321 is included in**  **this section (with HPLC methods) as no separate HPL C-MS section is listed.** 

6. Comment: **Commenter #4 recommended, regarding Chapter Two, Se ction 2.3.3, Page 10, third paragraph,**  **that the last sentence should include consulting Me thod 8000 prior to any HPLC-specific** 

**method as well. Recommended edit: Last sentence sh ould include consulting Method 8000**  **prior to any HPLC specific method as well.**

Response: **The Agency agrees and has amended paragraph three o f Section 2.3.3 of Chapter Two to state:**  **"Method 8000 gives a general description of the tec hniques of GC and HPLC. Method 8000**  **should be consulted prior to application of any of the GC or HPLC methods."** 

7. Comment: **Commenter #4 commented, regarding Chapter Two, Sect ion 2.3.3, that the four categories**  **discussed in the first paragraph do not make it cle ar where liquid chromatography (LC)/MS,**  **LC/MS/MS, and GC/time-of-flight (TOF) analyses fall . Recommended edit: Make it clear where**  **LC/MS, LC/MS/MS, and GC/TOF analyses fall.**

Response: **The Agency thanks the commenter for their input. L C/MS and LC/MS/MS (triple quadrupole)**  **are considered HPLC methods. GCs equipped with TOF mass spectrometers and triple**  **quadrupole mass spectrometers are considered part o f the GC/MS section. A short clarification**  **was added to Section 2.3.3 in the first paragraph.**

8. Comment:

**Commenter #4 commented, regarding Chapter Two, Sect ion 2.4.2, Page 74, Table 2-45 that**  **Synthetic Precipitation Leaching Procedure (SPLP) i s missing. Recommended edit: Add SPLP** 

**to this Section.**

Response: **The Agency agrees with the commenter and has added SPLP to Section 2.4.2.** 

9. Comment: **Commenter #4 commented, regarding Chapter Two, Tabl e 2-43, that the Table is missing** 

**Methods 8276 and 8430. Recommended edit: Add metho ds 8276 and 8430.** 

Response: **The Agency agrees with the commenter and has added Methods 8276 and 8430 to Table 2-43.** **Page 15**

10. Comment: **Commenter #4 commented, regarding Chapter Two, Tabl e 2-44, that the Table is missing** 

**Methods 3511 and 3572. Recommended edit: Add Metho ds 3511 and 3572.** 

Response: **The Agency thanks the commenter for their input, bu t disagrees with the commenter. Table 2-**  **44 (PREPARATION METHODS FOR INORGANIC ANALYSES) is correct. Methods 3511 and**  **3572 are both organics in nature and are included i n Table 2-41.** 

11. Comment: **Commenter #4 commented, regarding Chapter Two, Tabl es, that Table 2-1 is missing analytes**  **from Method 8276. The tables contains analytes not listed in the applicable method: Tables 2-**  **4, 2-6, 2-7, 2-20, 2-29; The Tables are missing an alytes listed in the applicable methods: Table**  **2-6, 2-20, 2-30, 2-31; The Tables list internal sta ndards or surrogates as target analytes: Tables**  **2-7; Tables do not contain analytes routinely analy zed for by users: Tables 2-10 (Aroclors 1262**  **and 1268). Analytes are not in alphabetical order. Recommended edit: Reconcile methods and** 

**tables.**

Response: **The Agency agrees with the commenter that Chapter 2 tables did not list all applicable**  **compounds presented in the associated methods, and that the compounds were not in**  **alphabetical order. Table 2-1 was revised to inclu de Method 8276 analytes. In addition,**  **Chapter 2 Tables were revised to include all compou nds listed in the most recent versions of the**  **referenced methods in alphabetical order. Extraneo us compounds (i.e., compounds not**  **included in the most recent versions of the applica ble methods) were removed from Chapter 2**  **tables. The Agency does not agree with the comment er on surrogates and internal standards**  **being listed in the Chapter 2 tables. As noted in the referenced methods, certain compounds**  **listed in the tables can be used as surrogates, but may also be analytes of interest.** 

**In addition, the Agency does not agree with the com menter on the issue of Chapter 2 tables not**  **containing analytes routinely analyzed. The Chapte r 2 tables contain all analytes discussed in**  **the applicable methods. While it is understood tha t additional compounds may be analyzed by**  **these methods, it is not EPA's intent to include al l possible compounds in the tables and thus**  **differ from the analytical methods. Users may anal yze other compounds by these methods, if**  **desired, as long as they can demonstrate adequate p erformance for that compound.** 

12. Comment: **Commenter #4 commented, regarding Chapter Two, Tabl es, that analyte tables for Methods**  **8323, 8440, 8520, 8276 are missing. Recommended ed it: Add tables for Methods 8323, 8440,**  **8520, and 8276.**

Response: **The Agency agrees with the commenter and has made t he requested edits. The following** 

**tables were added to address this comment: Table 2- 29A for Method 8323, Table 2-35A for**  **Method 8440, Table 2-36A for Method 8520 and Table 2-23A for Method 8276.** **Page 16** CHAPTER THREE

1. Comment: **Commenter #4 commented, regarding Chapter Three, th at for inorganics it states the mean**  **recovery should be +/- 35% with a relative standard deviation (RSD) of ≤20%. Then it states**  **that organics will vary more than inorganics but a limit of +/-20% is proposed until you develop**  **your own limits. That is more restrictive not less . Recommended edit: Resolve the**  **inconsistency between the statement that organics w ill show more variation than inorganics and** 

**the 20% limit.**

Response: **The Agency disagrees with the commenter. The LLOQ limits for inorganics and organics are**  **discussed in the Notice (on page 25), but not in Ch apters 3 or 4. The inorganic requirement is**  **±35% of the true value of the spike. The organic r equirement is ±20% of the LCS limits a**  **laboratory has in place, which should be a wider re covery limit for most compounds, but will**  **vary with each individual laboratory's statistical values.** 

2. Comment: **Commenter #3 noted, regarding Chapter Three, that c onsistency between Chapter 3 and**  **Methods 6010 and 6020 has been improved. They also applaud the approval of**  **collision/reaction cell technology for interference reduction in inductively coupled plasma**  **(ICP)/MS.**

Response: **The Agency thanks the commenter for their input.**

3. Comment: **Commenter #9 noted, regarding Chapter Three, FR Pag e 63191: thanks and congratulates the**  **Agency on improvements in consistency between Chapt er 3 and Methods 6010 and 6020 and**  **on the inclusion of collision cell approval.**

Response: **The Agency thanks the commenter for their input.**

4. Comment: **Commenter #4 commented, regarding Chapter Three, th e text for LLOQ states: "[LLOQ], which**  **is ideally less than or equal to the desired regula tory action levels based on the stated project**  **requirements." Recommended edit: The guidance shou ld provide clarification on how the LLOQ**  **is to be established in instances when regulatory l imits are much lower than the lowest** 

**calibration standard.**

Response: **The Agency appreciates the commenter's input, but d oes not currently publish directions for**  **how the individual laboratory determines their appr opriate LLOQ level for each instrument**  **and/or method used. The Chapters are intended as g eneral guidance. The details of how a**  **laboratory will determine its LLOQ levels should be included in the individual laboratory's quality**  **management plan (QMP) and in their SOPs for each me thod. If the LLOQ for a given method is**  **higher than the required regulatory limit, the user should select a different determinative method**  **(or a different preparation method) with an appropr iate LLOQ level for that user's need.** **Page 17**

5. Comment: **Commenter #4 commented, regarding Chapter Three, Se ction 3.3.2, the second to the last** 

**sentence in this Section includes a reference to "t rip blanks", which are only applicable to**  **volatiles analyses, not to inorganic analyses. Rec ommended edit: Remove "trip blanks" from** 

**the sentence.**

Response: **The Agency agrees with the commenter that trip blan ks are not commonly used in inorganic**  **analysis. The reference to trip blanks has been re moved from Chapter 3, Section 3.3.2.** 

6. Comment: **Commenter #4 commented, regarding Chapter Three, Ta ble 3-2, that the title of "Digestion**  **Volume" does not cover samples with solid matrices. Recommended edit: Change the title of**  **"Digestion Volume" to "Digestion Volume/Mass".**

Response: **The Agency agrees with the commenter and the reques ted edits were made to Table 3-2 of**  **Chapter 3. Page 18**  CHAPTER FOUR

1. Comment: **Commenter #4 commented, regarding Chapter 4, that f or inorganics it states the mean recovery** 

**should be +/- 35% with an RSD of ≤20%. Then it sta tes that organics will vary more than**  **inorganics but a limit of +/-20% is proposed until you develop your own limits. That is more** 

**restrictive not less. Recommended edit: Resolve th e inconsistency between the statement that**  **organics will show more variation than inorganics a nd the 20% limit.** 

Response: **The Agency disagrees with the commenter. The LLOQ limits for inorganics and organics are**  **discussed in the Notice (on page 25) and in the met hods, but not in Chapters 3 or 4. The**  **inorganic requirement is ±35% of the true value of the spike. The organic requirement is ±20%**  **of the LCS limits a laboratory has in place, which should be a wider recovery limit for most**  **compounds, but will vary with each individual labor atory's statistical values.** 

2. Comment: **Commenter #2 commented, regarding Chapter 4, Table 4-1, that for volatile organics analyses**  **(VOAs), "If compounds that readily degrade in acidi fied water (e.g., 2-chloroethyl vinyl ether) are**  **analytes of interest, collect a second set of sampl es without acid preservatives and analyze as**  **soon as possible." The table shows a holding time of 7 days for such analyses.** 

**Footnote b to the table reads: "See References 1-1 0 for the preservation and holding times**  **studies for volatile organics and the January and F ebruary 2012 RCRA Organic Workgroup**  **discussion for preservation and holding times for v inyl chloride, styrene and 2-chloroethyl vinyl**  **ether in aqueous samples." References 15, 16 and 1 7 then list the RCRA Organic Methods**  **Workgroup Meeting Minutes from January 19, 2012, Ja nuary 26, 2012 and February 9, 2012.** 

**From this combination of information, it is not cle ar whether the intended guidance is for**  **collection of a second set of unpreserved samples o nly in cases where 2-chloroetyhyvinyl ether**  **is an analyte of interest, or whether a second set of unpreserved samples should be collected**  **when 2-chloroethyl vinyl ether, vinyl chloride or s tyrene are among the analytes of interest. The**  **table should be revised to clarify the intent of th e guidance.** 

**The January and February 2012 RCRA Organics Workgro up Meeting Minutes from January 19,**  **January 2 and February 9, 2012 are not publically a vailable. EPA should either make these**  **available, include the pertinent information from t hem in Chapter 4, or refrain from citing them as** 

**references. If the content of the references is no t available, the references are useless.** 

Response: **The Agency agrees with the commenter and has placed the January 19, 26 and February 9,** 

**2012 minutes in the Docket.**

**Footnote b of Table 4-1 has been revised to read: " See References 1-10 for the preservation**  **and holding times studies for volatile organics. I t is the intention of the Agency that separate,**  **unpreserved vials be collected when 2-chloroethylvi nyl ether is an analyte of interest."** **Page 19**

3. Comment: (The Agency received two similar commen t on volatile preservation. They are answered here together.)

**Commenter #3 commented, regarding Chapter 4, that w e approve of the removal of the**  **requirement to analyze vinyl chloride and styrene f rom an unpreserved sample in Chapter 4.**  **Both compounds have been demonstrated to be stable at pH 2. However we noted that the**  **same change had not been made for soil samples, and request the following change in the**  **volatile organics, solid samples Section of Table 4 .1 of Chapter 4: If compounds that may be**  **reactive in acidified soils (e.g., vinyl chloride, styrene, 2-chloroethyl vinyl ether) are analytes of**  **interest, do not use acid preservation options. Co llect a second set of samples without acid**  **preservatives and analyze as soon as possible.**

**and**

**Commenter #9 commented, regarding Chapter 4, FR pag e 63191: Previous versions of Chapter**  **4 stated that vinyl chloride and styrene had to be analyzed from an unpreserved vial. EPA**  **responded by removing the requirement in Chapter 4, for aqueous samples. This is a positive**  **change; however, styrene and vinyl chloride should also be removed from the following**  **statement for solid samples: "If compounds that ma y be reactive in acidified soils (e.g., vinyl**  **chloride, styrene, 2-chloroethyl vinyl ether) are a nalytes of interest, collect a second set of**  **samples without acid preservatives and analyze as s oon as possible."** 

Response: **The Agency removed the requirement for vinyl chlori de and styrene in a water matrix after**  **reviewing performance data from a study that was re ceived by ORCR. In order to remove the**  **requirement for soils, the Agency welcomes data fro m a similar study demonstrated for solid**  **matrices. The Agency still recommends a second unp reserved set of samples be taken any**  **time 2-chloroethylvinyl ether is a target compound.**

4. Comment: **Commenter #9 commented, regarding Chapter 4, FR (on page 63191), that they thank and**  **congratulate the Agency on the removal of the requi rement for a separate sample for styrene**  **and vinyl chloride in Chapter 4.**

Response: **The Agency appreciates the input.**

5. Comment: **Commenter #4 commented, regarding Chapter 4, Sectio n 4.1.6, Page FOUR-7, Step 3: Please**  **note that both AlconoxTM and SparkleenTM contain a su bstantial amount of phosphate, and are**  **not recommended for the phosphate-free decontaminat ion applications prescribed in Section**  **3.3.3 of SW-846 Chapter Three. When a phosphate-fr ee detergent is recommended, AlconoxTM**  **and SparkleenTM should not be used. LiquinoxTM, whic h does not contain phosphate, should be**  **used. Recommended edit: Suggest that the last two sentences about AlconoxTM and**  **SparkleenTM be deleted. Or, delete the last sentenc e and change "Alconox" to "LiquinoxTM",**  **and explain that LiquinoxTM is a phosphate-free dete rgent that will not cause false positives for**  **phosphate analysis or contribute to excess weed gro wth in surface water.** 

Response: **Chapter 4 deals with organic analyses and as such, phosphate contamination is not a primary**  **concern. Any detergents used by the laboratories s hould be eliminated during the washing and** **Page 20**

**thorough rinsing process. It is up to the individu al laboratories to select whatever detergents**  **best suit their cleaning needs. If phosphates are concern to the analysis, a low phosphate or**  **phosphate-free detergent would be most appropriate.**

6. Comment: **Commenter #4 commented, regarding Chapter 4, Sectio n 4.3.2, Method 8276 should be** 

**included in the list of methods in this Section. R ecommended edit: Add method 8276 to the list** 

**of methods in this Section.**

Response: **The Agency agrees with the commenter and has added Method 8276 to Table 4.3.2.** 

7. Comment: **Commenter #4 asked, regarding Chapter 4, Section 4. 3.3, should method 8330A be changed to** 

**8330B in the list of methods in this Section? Or sh ould method 8330B be included in the list?**  **Recommended edit: Replace or add method 8330B to th e list of methods in this Section.** 

Response: **The Agency disagrees with the commenter as 8330A is the current published method. We will**  **revisit and publish 8330B when time and resources a llow in the future.** 

8. Comment: **Commenter #4 commented, regarding Chapter 4, Table 4-1, Pages FOUR-11 & FOUR-12,**  **Aqueous samples: Aqueous samples should not be coo led to ≤ 6 °C (i.e., < 0 °C) and frozen.**  **Also, suggest that "3 x 40-mL vials" be collected. To avoid potential breakage of 1-L glass**  **containers due to frozen water, aqueous samples sho uld be cooled to 0 - 6 °C. Recommended**  **edit: Change "≤ 6 °C" to "0 - 6 °C" and "2 x 40-mL" to "3 x 40-mL".** 

Response: **The Agency agrees with the commenter and has made t he proposed edits.** 

9. Comment: **Commenter #4 commented, regarding Chapter 4, Table 4-1, Pages FOUR-9 & FOUR-10,**  **Aqueous VOC samples: Aqueous samples should not be cooled to ≤ 6 °C (i.e., < 0 °C) and**  **frozen. Also, suggest that "3 x 40-mL vials" be co llected. To avoid potential VOC vial breakage**  **due to frozen water, aqueous samples should be cool ed to 0 - 6 °C. Also, recommend that 3 x**  **40-mL vials be collected for the initial sample scr eening, sample analysis, and sample re**  **analysis, if needed. Recommended edit: Change "≤ 6 °C" to "0 - 6 °C" and "2 x 40-mL" to "3 x** 

**40-mL".**

Response: **The Agency agrees with the commenter and has made t he proposed edits.** **Page 21** CHAPTER NINE

1. Comment: **Commenter #9 commented, regarding Chapter One and C hapter Nine, that additional guidance**  **has been provided in the proposed revision of Chapt er 1 (including references) regarding the**  **calculation of the UCL for making the determination as to whether a waste may be hazardous.**  **Specifically, in Section 1.1.3.2 of Chapter 1, seve ral documents are listed for the development**  **of Sampling and Analysis Plans. At least two of th ese documents contradict one another in their**  **use of the UCL for making the determination that th e analytical results for a given waste could** 

**exceed the RCRA limit.**

**• In SW-846, Chapter 9, Page 16, starting in Sectio n 7 and Equation 6 (which is repeated**  **multiple times in Chapter 9), the two-tailed critic al value for the Student's t distribution is used.** 

**• In Chapter 1, Reference 8, "RCRA Waste Sampling D raft Technical Guidance" (EPA 503-D**  **02-002), in Section 3.4.3.1, Appendices F (Equation F.6) and G (Table G-1) the single-tailed** 

**critical value for the Student's t distribution is used.** 

**The commenter believes that use of the single-taile d critical value is statistically correct and**  **asks that either Chapter 9 be revised to utilize th e single-tailed critical value for the UCL or the**  **conflicting references in Chapter 1 be removed.**

Response:

**Chapter 9 is not included in Update V and as such, is not subject to revision at this time. The**  **Agency thanks the commenter for their input and the comment will be discussed the next time**  **Chapter 9 is updated. Page 22**  METHOD 3200

1. Comment: **Commenter #4 commented, regarding Method 3200, Sect ion 11.2.1.4, that the Section states**  **cold sample storage requirements "Store extracts in the cold at 4 °C until analysis". The current**  **storage requirements as stated in Chapter 3 are to "store extracts in the cold at ≤6 °C until**  **analysis." Recommended edit: Update from old requi rements (4 °C) to new requirements (≤6**  **°C).**

Response: **The Agency agrees with the commenter and has made t he requested change in Method 3200,** 

**Section 11.2.1.4.**

**The rest of the Update V methods were searched and the same temperature range correction**  **was made in Method 8410 (Section 7.4.2) and Method 8430 (Sections 7.5.2, 8.2 and 11.3.4).** **Page 23** METHOD 6010D

1. Comment: **Commenter #4 commented, regarding Method 6010D, tha t the text states: "In the absence of**  **project-specific DQOs, the method blank may be cons idered to be acceptable with respect to**  **each target element, if it is less than the LLOQ, 5 0% of the regulatory limit, or 10% of the lowest**  **sample concentration, whichever is greater." Recom mended edit: Define if the "lowest sample**  **concentration" is relative to the sample delivery g roup (SDG), batch, or site samples.** 

Response: **The Agency believes that guidance in this section i s clear and refers to**  analytical batch **. Refer to the subsequent sentences of this paragraph as fo**  **llows: "If the method blank fails to meet the necessary acceptance criteria, it should be re-anal**  **yzed once. If still unacceptable, then all samples associated with the method blank must be re**  **-prepared and re-analyzed, along with all other appropriate**  analysis batch **QC samples". Also refer to the previous language in section**  **9.7: "At a minimum, this should include the analysi s of QC samples including a method blank, a**  **matrix spike (MS), a laboratory control sample (LCS ), and a duplicate sample in each**  analytical

batch **".**

2. Comment: **Commenter #7 commented, regarding Method 6010D, reg arding method blank (Section 9.7.1):**  **In the absence of project level DQOs, the method bl ank may be considered to be acceptable if**  **< LLOQ or < 50% of regulatory limit or < 10% of the lowest sample concentration, whichever is**  **greater. This guidance should be revised such that if there is no regulatory limit and the method**  **blank is >10% of the lowest sample concentration, t hen the method blank must be less than**  **50% of the LLOQ to avoid significant bias for sampl es near the LLOQ. Allowing a method blank**  **to be at the LLOQ would significantly bias the samp le results near the LLOQ.** 

Response: **The Agency disagrees and contends that if there is no regulatory limit and the method blank is**  **>10% of the lowest sample concentration, then the m ethod blank may be considered to be**  **acceptable if <LLOQ.**

3. Comment: **Commenter #7 asked, regarding Method 6010D (Section 9.7.3): Is there an error in line 6 of the**  **2nd paragraph? Should "method blank" be changed to "LCS"? In this same section of 6010C,** 

**the term LCS was used.**

Response: **The Agency confirms there is no error and "method b lank" is correct as it helps define the**  **analytical batch associated with the unacceptable L CS.** 

4. Comment: **Commenter #7 commented, regarding Method 6010D (Sec tion 9.11.1): If the analyte**  **concentration is within the linear range of the ins trument and sufficiently high (minimally, a factor**  **of 25 times greater than the LLOQ), an analysis of a 1:5 dilution should agree to within ± 20% of**  **the original determination. The acceptance limit o f +/- 10% of the original determination should**  **be maintained (same limits as Method 6010C). Respo nses that are outside +/- 10% of the**  **original response are likely biased by the sample m atrix.** **Page 24**

Response: **The Agency disagrees and contends that concentratio ns that are outside +/- 20% of the original**  **determination are likely biased by the sample matri x. This method is intended as guidance.**  **The analytical laboratory may use tighter QC limits than specified in the method (such as ±10%)**  **if their regulatory body recommends them or if they have a good reason to do so.** 

5. Comment: **Commenter #4 commented, regarding Method 6010D, Sec tions 4.1.1.2 & 9.6**  **that "analytical range" is not well defined in the SW-846 and is not**  **commonly used by the environmental labs. Recommended edit: Change the "analytical range" to**  **"quantitation range" or "calibration range".**

Response: **The Agency appreciates this comment; however, the A gency feels the term "analytical range" is**  **adequately defined in describing how to mitigate sp ectral interferences, which is the major**  **emphasis of section 4.1.1.2. "Analytical range" is not mentioned in Section 9.6.** 

6. Comment: **Commenter #4 recommended, regarding Method 6010D, S ection 7.9, correct the typo of "105**  **EC". Recommended edit: Change "105 EC" to "105 °C"**

**.**

Response: **The Agency agrees with the commenter's suggested co rrection. "105 EC" in Section 7.9 has**  **been changed to "105 °C".**

7. Comment: **Commenter #4 commented, regarding Method 6010D, Sec tion 7.9.24, that silver standard**  **solutions should be protected from light. Silver i ons may precipitate out from solution if exposed**  **to light. Recommended edit: Request that silver st andard solutions be protected from light by**  **storing in a dark room or wrapping the standard con tainers with aluminum foils.** 

Response: **The Agency agrees with the commenter's suggested ed it. The following sentence has been**  **added to Section 7.9.24: "Protect standard from lig ht during storage."** 

8. Comment: **Commenter #4 recommended, regarding Method 6010D, S ection 9.3, provide the detailed**  **procedures for calculating the IDL. The procedures for determining IDL are not provided in the**  **SW-846. Recommended edit: Please provide the proce dures or references for determining and**  **calculating an IDL for metals analysis.**

Response: **The Agency thanks the commenter for their input; ho wever, the Agency feels the procedures for**  **calculating the IDL are sufficiently described in S ection 9.3 as follows: "IDLs in μg/L can be**  **estimated as the mean of the blank results plus thr ee times the standard deviation of 10**  **replicate analyses of the reagent blank solution. (Use zero for the mean if the mean is**  **negative)".**

9. Comment: **Commenter #4 commented, regarding Method 6010D, Sec tion 9.8.2, that more details on LLOQ**  **verifications are needed. The frequency LLOQ verif ications for infrequently run analyses should** 

**be increased to establish in-house control limits. The logistics on LLOQ verifications with** **Page 25**

**sample matrices should also be addressed. Recommen ded edit: More guidance should be**  **provided.**

Response: **The Agency believes the method provides adequate gu idance on LLOQ verifications. The**  **method allows for more frequent LLOQ verifications by only specifying a minimum frequency.**  **Logistics are not detailed to allow options for lab oratories to use a clean control material or a**  **representative sample matrix (free of target compou nds) to achieve LLOQ verifications less than**  **the desired regulatory action levels or based on th e stated project-specific requirements.** 

10. Comment: **Commenter #4 commented, regarding Method 6010D, Sec tions 10.8.4 and 10.8.5, and Method**  **6020B, Sections 10.5.4 and 10.5.5, that Sections 10 .8.4 and 10.5.4 address the analysis and**  **acceptance criteria for the initial calibration bla nk (ICB), as in the following paragraph: "Initial**  **Calibration Blank (ICB) - If a multi-level calibrat ion is used, an ICB is analyzed immediately after**  **the calibration (or after the ICV) and must not con tain analytes above half the LLOQ. If a single**  **point calibration is used, the calibration is force d through the ICB, but a second ICB is analyzed**  **as a check and must not contain target analytes abo ve half the LLOQ." Sections 10.8.5 and**  **10.5.5 address the analysis of and acceptance crite ria for continuing calibration blanks (CCBs).**  **The CCB acceptance criteria is that the CCB must no t contain target analytes > the LLOQ,**  **which differs from the ICB acceptance criteria. Se ction 10.8.5 then contains this sentence: "If**  **the ICB consistently has target analyte concentrati ons greater than half the LLOQ, the LLOQ** 

**should be re-evaluated." The last sentence would m ake more sense in Section 10.8.4, where**  **the ICB analysis and acceptance is addressed. Reco mmended edit: Move the following** 

**sentence from Sections 10.8.5 and 10.5.5 to 10.8.4 and 10.5.4: "If the ICB consistently has**  **target analyte concentrations greater than half the LLOQ, the LLOQ should be re-evaluated."** 

**Do NOT include a similar sentence in 10.8.5 or 10.5 .5.** 

Response: **The Agency agrees with the recommended edit to move the sentence: "If the ICB consistently**  **has target analyte concentrations greater than half the LLOQ, the LLOQ should be re** 

**evaluated" from Section 10.8.5 to Section 10.8.4. The Agency acknowledges and confirms that**  **the acceptance criteria for the CCB differ from the acceptance criteria for the ICB.** 

11. Comment: **Commenter #4 commented, regarding Method 6010D, Sec tion 7.10, and 6020B, Section 7.27,**  **that the following sentence does not make sense: "I f the determination of one or more metals**  **using a non-aqueous solvent is required, then all s tandards and quality control samples must be**  **prepared on a weight/weight basis in the non-aqueou s solvent since the density of non-aqueous**  **solvents is not unity." Recommended edit: Change t he sentence to: "If the determination of one**  **or more metals using a non-aqueous solvent is requi red, then all standards and quality control**  **samples must be prepared on a weight/weight basis i n the non-aqueous solvent since the**  **density of non-aqueous solvents is not uniform."**

Response: **The Agency agrees with the commenter's recommended edit. The word "unity" in Method**  **6010D, Section 7.10, and Method 6020B, Section 7.27 has been changed to "uniform".** 

12. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 9.4.2.1, and Method 6010D,**  **Section 9.7.2 ,that the "1 - 5 times the background concentration" is not always appropriate. If** **Page 26**

**the background concentration is very low or non-det ect (e.g., organic analytes), any spike**  **amount may lead to a ratio between the spike concen tration and the background concentration**  **> 5; however, the MS/MSD data are generally useable . Recommended edit: Suggest that a**  **NOTE such as "NOTE: If the background sample concen tration is very low or non-detect, a**  **spike of greater than 5 times the background concen tration is still acceptable. To assess data**  **precision with duplicate analyses, it is preferred to use a low concentration field sample to**  **prepare MS/MSD for organic analyses and a high conc entration field sample to prepare**  **unspiked laboratory duplicates for metals analyses. "** 

Response:

**The Agency agrees with the commenter and has revise d the note in Section 9.7.2 of 6010D and**  **6020B: "NOTE: If the background sample concentrati on is very low or non-detect, a spike of**  **greater than 5 times the background concentration i s still acceptable. To assess data precision**  **with duplicate analyses, it is preferable to use a high concentration field sample to prepare**  **unspiked laboratory duplicates for metals analyses. "** 

Comments on 6010D received after Public Comment per iod was over:

**Comment #2, regarding Methods 6010D, Section 9.6 an d 6020B, Section 9.6: Running a linear**  **range on each run puts every sample at risk of a fa lse positive due to carry-over that cannot be**  **distinguished from low level analyte in the sample. Running a linear range on each run also**  **significantly increases out of specifications for i nitial and continuing check blanks, as well as**  **method blanks, due to carry-over. Any individual s ample can randomly contain high levels of**  **analyte and cause this issue, but analyzing a linea r range on every run elevates the risk.** 

**Response: The Agency thanks the commenter for their input; ho**  **wever, Section 9.6 of Method 6010D and Section 9.6 of Method 6020B do not require the anal**  **ysis of a higher standard to extend the linear range, but gives the laboratory the option t**  **o do so. A laboratory should not run a high level linear range standard if doing so produces me**  **mory effects that affect lower level readings. The laboratory can go with the option of demonstrat**  **ing linearity up to their highest calibration standard and dilute if any samples are out of the c**  **alibration range.**

**Comment #3, regarding Methods 6010D, Sections 9.9.1 and 9.9.2 and Method 6020B, Section**  **9.9: The analysis of a SIC (Spectral Interference Check) has contradictory wording in Method**  **6010D. Section 9.9.1 says single element checks sh ould be < 2x the LOQ, Section 9.9.2 says** 
**that multi element SIC should be < LOQ. Previous m ethods require < 2x LOQ. The**  **requirement of < LOQ in a solution with interferenc es in this range will require that laboratories**  **raise their routine LOQs in order to pass this more restrictive requirement. Raised LOQs are**  **contradictory to the requirements requested by most clients.** 

**Response: The Agency thanks the commenter for their input; ho**  **wever the requirement for the mixed**

**element SIC solution in Section 9.9.2 of Method 601 0D is +/- the LLOQ and not <LLOQ as**  **stated in the comment. The requirement for the mix ed element SIC is to ensure interference**  **corrections are in control on a regular basis. The laboratory also has the option of raising the** 
**LLOQ to twice the concentration measured in the mix ed element SIC solution. The requirement** 

**for the mixed element SIC solution in Section 9.9 o f Method 6020B is stated as <2x the LLOQ.** **Page 27** METHOD 6020B

1. Comment: **Commenter #4 commented, regarding Method 6020B, Sec tions 10.5.4 and 10.5.5, and 6010D,**  **Sections 10.8.4 and 10.8.5, that Sections 10.8.4 an d 10.5.4 address the analysis and**  **acceptance criteria for the ICB, as in the followin g paragraph: "Initial Calibration Blank (ICB) - If**  **a multi-level calibration is used, an ICB is analyz ed immediately after the calibration (or after the**  **ICV) and must not contain analytes above half the L LOQ. If a single point calibration is used,**  **the calibration is forced through the ICB, but a se cond ICB is analyzed as a check and must not**  **contain target analytes above half the LLOQ." Sect ions 10.8.5 and 10.5.5 address the analysis**  **of and acceptance criteria for continuing calibrati on blanks (CCBs). The CCB acceptance**  **criteria is that the CCB must not contain target an alytes > the LLOQ, which differs from the ICB**  **acceptance criteria. Section 10.8.5 then contains this sentence: "If the ICB consistently has**  **target analyte concentrations greater than half the LLOQ, the LLOQ should be re-evaluated."** 

**The last sentence would make more sense in Section 10.8.4, where the ICB analysis and**  **acceptance is addressed. Recommended edit: Move th e following sentence from Sections** 

**10.8.5 and 10.5.5 to 10.8.4 and 10.5.4: "If the ICB consistently has target analyte**  **concentrations greater than half the LLOQ, the LLOQ should be re-evaluated." Do NOT include** 

**a similar sentence in 10.8.5 or 10.5.5**

Response: **The Agency agrees with the recommended edit to move the sentence: "If the ICB consistently**  **has target analyte concentrations greater than half the LLOQ, the LLOQ should be re** 

**evaluated." from Section 10.5.5 to Section 10.5.4. The Agency acknowledges and confirms that**  **the acceptance criteria for the CCB differ from the acceptance criteria for the ICB.** 

2. Comment: **Commenter #4 commented, regarding Method 6020B, Sec tion 7.27, and 6010D, Section 7.10,**  **that the following sentence does not make sense: "I f the determination of one or more metals**  **using a non-aqueous solvent is required, then all s tandards and quality control samples must be**  **prepared on a weight/weight basis in the non-aqueou s solvent since the density of non-aqueous**  **solvents is not unity." Recommended edit: Change t he sentence to: "If the determination of one**  **or more metals using a non-aqueous solvent is requi red, then all standards and quality control**  **samples must be prepared on a weight/weight basis i n the non-aqueous solvent since the**  **density of non-aqueous solvents is not uniform."**

Response: **The Agency agrees with the commenter's recommended edit. The word "unity" in Method**  **6020B, Section 7.27, and Method 6010D, Section 7.10 has been changed to "uniform".** 

3. Comment: **Commenter #7 commented, regarding Method 6020B (Sec tion 9.7.1): In the absence of project**  **level DQOs, the method blank may be considered to b e acceptable if < LLOQ or < 50% of**  **regulatory limit or <10% of the lowest sample conce ntration, whichever is greater. This**  **guidance should be revised such that if there is no regulatory limit and the method blank is**  **>10% of the lowest sample concentration, then the m ethod blank must be less than 50% of the**  **LLOQ to avoid significant bias for samples near the LLOQ. Allowing a method blank to be at**  **the LLOQ would significantly bias the sample result s near the LLOQ.** **Page 28**

Response: **The Agency disagrees and contends that if there is no regulatory limit and the method blank is**  **>10% of the lowest sample concentration, then the m ethod blank may be considered to be**  **acceptable if < LLOQ.**

4. Comment: **Commenter #7 commented, regarding Method 6020B (Sec tion 9.10): The intensities of each**  **internal standard must be monitored for every analy sis to ensure that it does not decrease**  **below 30%, with respect to its intensity during the initial calibration. Allowing up to a 70% drop**  **in response will significantly compromise the sensi tivity of the analysis. A lower limit of 50% in**  **internal standard response would be more appropriat e.** 

Response: **The Agency believes the commenter is misinterpretin g the criterion. The criterion allows up to a**  **30% drop in response. As an example, if the initia l calibration internal standard response is**  **100,000 counts per second (cps), anything below 70, 000 cps in the sample would be**  **unacceptable. The text from 9/10 of 6020B currentl y states: "The intensities of each internal**  **standard must be monitored for every analysis to en sure that it does not decrease below 30%,**  **with respect to its intensity during the initial ca libration."** 

5. Comment: **Commenter #7 commented, regarding Method 6020B (Sec tion 9.13.1): If the analyte**  **concentration is within the linear range of the ins trument and sufficiently high (minimally, a factor**  **of 25 times greater than the LLOQ), an analysis of a 1:5 dilution should agree to within ± 20% of**  **the original determination. The acceptance limit o f +/- 10% of the original determination should**  **be maintained (same limits as method 6020A). Respo nses that agree to only +/- 11% thru +/-**  **20% are likely biased by the sample matrix.**

Response: **The Agency disagrees and contends that concentratio ns that are outside +/- 20% of the original**  **determination are likely biased by the sample matri x. This method is intended as guidance.**  **The analytical laboratory may use tighter QC limits than specified in the method (such as ±10%)**  **if their regulatory body recommends them or if they have a good reason to do so.** 

6. Comment: **Commenter #7 commented, regarding Method 6020B (Sec tion 10.4): If a multipoint calibration**  **is used, the low standard must be at or below the L LOQ. There may be situations where the**  **low standard could be above the LLOQ. The wording should be changed from "must" to**  **"should". If the LLOQ is not on the curve, an LLOQ Check Standard should be analyzed and**  **evaluated against the curve. We recommend a limit of +/- 20%.** 

Response: **The Agency disagrees. The Agency believes the low standard should be representative of a**  **concentration at or below the laboratory's LLOQ; th erefore there will be no situations where the**  **low standard of a multipoint calibration could be a bove the LLOQ. For all multipoint calibration**  **scenarios, the lowest non-zero standard concentrati on should be considered the LLOQ.** 

7. Comment: **Commenter #7 commented, regarding Method 6020B (Sec tion 11.4): Replicate scans of the**  **tuning solution should be required to confirm the i nstrument is stable (≤5% RSD), as per Method** 

**6020A. Page 29** 

Response: **The Agency appreciates this comment; however, repli cate scans of the tuning solution were**  **eliminated to allow the laboratory the ability to d etermine instrument stability.** 

8. Comment: **Commenter #4 commented, regarding Method 6020B, Sec tion 1.2, Page 2 of the method, below**  **the table of analytes, that the term "inductively c oupled plasma-atomic emission spectrometry"**  **is used, when, in Method 6010D all references to th at term have been changed to "inductively**  **coupled plasma-optical emission spectrometry." Rec ommended edit: Change all references in**  **6020B from "inductively coupled plasma-atomic emiss ions spectrometry" to inductively coupled**  **plasma-optical emission spectrometry."**

Response: **The Agency agrees with the commenter's recommended edit. The term "inductively coupled**  **plasma-atomic emission spectrometry" in Method 6020 B, Section 1.2, below the table of**  **analytes, has been changed to the term "inductively coupled plasma-optical emission**  **spectrometry."**

9. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 9.4.2.1, and Method 6010D,**  **Section 9.7.2 , that the "1 - 5 times the backgroun d concentration" is not always appropriate. If**  **the background concentration is very low or non-det ect (e.g., organic analytes), any spike**  **amount may lead to a ratio between the spike concen tration and the background concentration**  **> 5; however, the MS/MSD data are generally useable . Recommended edit: Suggest that a**  **NOTE such as "NOTE: If the background sample concen tration is very low or non-detect, a**  **spike of greater than 5 times the background concen tration is still acceptable. To assess data**  **precision with duplicate analyses, it is preferred to use a low concentration field sample to**  **prepare MS/MSD for organic analyses and a high conc entration field sample to prepare**  **unspiked laboratory duplicates for metals analyses. "** 

Response:

**The Agency agrees with the commenter and has revise d the note in Section 9.7.2 of 6020B:**  **"NOTE: If the background sample concentration is v ery low or non-detect, a spike of greater**  **than 5 times the background concentration is still acceptable. To assess data precision with**  **duplicate analyses, it is preferable to use a high concentration field sample to prepare unspiked**  **laboratory duplicates for metals analyses."**

Comments on 6020B received after Public Comment per iod was over:

**Comment #2, regarding Methods 6010D, Section 9.6 an d 6020B, Section 9.6: Running a linear**  **range on each run puts every sample at risk of a fa lse positive due to carry-over that cannot be**  **distinguished from low level analyte in the sample. Running a linear range on each run also**  **significantly increases out of specifications for i nitial and continuing check blanks, as well as**  **method blanks, due to carry-over. Any individual s ample can randomly contain high level of**  **analyte and cause this issue, but analyzing a linea r range on every run elevates the risk.** 

**Response: The Agency thanks the commenter for their input; ho**  **wever, Section 9.6 of Method 6010D and Section 9.6 of Method 6020B do not require the anal**  **ysis of a higher standard to extend the linear range, but gives the laboratory the option t**  **o do so. A laboratory should not run a high- Page 30** 

**level linear range standard if doing so produces me mory effects that affect lower level readings.**  **The laboratory can go with the option of demonstrat ing linearity up to their highest calibration**  **standard and dilute if any samples are out of the c alibration range.** 

**Comment #3, regarding Methods 6010D, Sections 9.9.1 and 9.9.2 and Method 6020B, Section**  **9.9: The analysis of a SIC (Spectral Interference Check) has contradictory wording in Method**  **6010D. Section 9.9.1 says single element checks sh ould be < 2x the LOQ, Section 9.9.2 says** 
**that multi element SIC should be < LOQ. Previous m ethods require < 2x LOQ. The**  **requirement of < LOQ in a solution with interferenc es in this range will require that laboratories**  **to raise their routine LOQs in order to pass this m ore restrictive requirement. Raised LOQs are**  **contradictory to the requirements requested by most clients.** 

**Response: The Agency thanks the commenter for their input; ho**  **wever the requirement for the mixed**

**element SIC solution in Section 9.9.2 of Method 601 0D is +/- the LLOQ and not <LLOQ as**  **stated in the comment. The requirement for the mix ed element SIC is to ensure interference**  **corrections are in control on a regular basis. The laboratory also has the option of raising the** 
**LLOQ to twice the concentration measured in the mix ed element SIC solution. The requirement** 

**for the mixed element SIC solution in Section 9.9 o f Method 6020B is stated as <2x the LLOQ.** 

Comment from the Method Information Communication E xchange (MICE) line:

**The only item that remains a little unclear is what defines "official" with regard to a version of**  **6020B. The Federal Register notice of 10/23/13 whi ch made available 6020B, Revision 2,**  **October 2012 states, "Update V contains 23 new and revised analytical methods that the**  **Agency has evaluated, and which may be used for mon itoring or complying with the RCRA**  **hazardous and non-hazardous waste regulations". I can appreciate that the methods were**  **issued with the need for a public comment period, a fter which the methods could be changed**  **yet again. However, there is some level of "offici alness" if the Agency has declared these**  **methods suitable for use in complying with RCRA. T his of course is in agreement with the core**  **philosophy of SW846 methods being guidance document s in the first place.** 

**The only other item we found yesterday was that Tab le 2 Recommended Elemental Isotopes for**  **Selected Elements is missing one of the most import ant isotopes for molybdenum (Mo) at mass**  **95. This may not be the most abundant Mo isotope b ut it is the most abundant Mo isotope that**  **does not require isobar corrections. Even though i t is only in Table 2 as a potential interferent,**  **when it is quantified as an analyte it might be ben eficial to use Mo-95.** 

**Response: The draft version of 6020B found on the Federal Reg**  **ister notice should not be considered final. It was a draft for public comment. The official re**  **lease of 6020B will be with Update V with all the public comments addressed. The updated methods wil**  **l have a July 2014 date in the footer. The Agency agrees with the comment and has added Mo**  **-95 as an analytical mass to Table 2. Page 31**  METHOD 8000D

1. Comment: **Commenter #3 commented, regarding Method 8000D, tha t they approve of the use of LCS** 

**limits with an additional +/- 20% as a reasonable w ay to set initial limits for LLOQ standards.** 

Response: **The Agency thanks the commenter for their input.**

2. Comment: **Commenter #3 commented, regarding Method 8000D, tha t clarifications to the initial**  **demonstration of proficiency requirements are usefu l and will serve to improve consistency in**  **the ways that laboratories approach their demonstra tions of capability.** 

Response: **The Agency thanks the commenter for their input.**

3. Comment: **Commenter #3 commented, regarding Method 8000D, tha t they strongly approve of the addition**  **of relative standard error (RSE) as a method for ev aluation of calibration curves, and appreciate**  **the consistency with similar approval in CFR 40 Par t 136.** 

Response: **The Agency thanks the commenter for their input.**

4. Comment: **(Note: The Agency received two similar comments on this Section. They have**  **been listed together as the response covers both it ems.)** 

**Commenter #7 commented, regarding Method 8000D (Sec tion 9.2.6.7): The LLOQ may be**  **raised to 5x the method blank response to avoid rep orting false positives. This allowance to** 
**elevate the LLOQ for individual data sets due to la b contamination may be inappropriate for** 
**some data sets. The elevated LLOQ could mask the m ethod blank response and make it**  **appear that sample responses just above the LLOQ we re unbiased by lab contamination. The**  **preferred approach would be to determine an LLOQ th at is consistently 5x greater than lab** 

**contamination. Data sets where the method blank ex ceeds that LLOQ should have appropriate** 

**corrective actions taken and then if the blank is s till greater than the LLOQ, the sample results**  **should be appropriately qualified.**

**and**

**Commenter #4 commented, regarding Method 8000D, Sec tion 9.2.6.7, note, that the analyst**  **may raise the LLOQ to 5x the blank concentration to avoid reporting false positive results. If the**  **LLOQ is raised, the precision and bias should be up dated. Recommended edit: Add statement**  **that: When raising the LLOQ to 5x the blank concent ration, the precision and bias must be**  **updated as well.**

Response: **The note in 8000D Section 9.2.6.7: "NOTE: The analy st may raise the LLOQ to 5x the blank**  **concentration to avoid reporting false positive res ults" was removed and replaced by the**  **following language, which was discussed and approve d by the work group:** **Page 32**

**9.2.6.9 Blanks are generally considered to be accep table if target analyte concentrations are**  **less than one-half the LLOQ or are less than projec t-specific requirements. Blanks may contain**  **analyte concentrations greater than acceptance limi ts if the associated samples in the batch are**  **unaffected (i.e., targets are not present in sample s or sample concentrations are ≥10X the**  **blank). Other criteria may be used depending on th e needs of the project.** 

**9.2.6.10 If an analyte of interest is found in a sa mple in the batch near a concentration**  **confirmed in the blank (refer to Sec. 9.5.2), the p resence and or/concentration of that analyte**  **should be considered suspect and may require qualif ication. Contaminants in the blank should**  **meet most or all of the qualitative identifiers in Section 11.6 to be considered. Samples may**  **require re-extraction and/or re-analysis if the bla nks do not meet lab established or project**  **specific criteria. Re-extraction and/or re-analysi s is not necessary if the analyte concentration**  **falls well below the action or regulatory limit or if the analyte is deemed not important for the**  **project.**

**9.2.6.11 When new reagents or chemicals are receive d, the lab should monitor the blanks**  **associated with samples for any signs of contaminat ion. It is not necessary to test every new**  **batch of reagents or chemicals prior to sample prep aration if the source shows no prior**  **problems. However, if reagents are changed during a preparation batch, separate blanks need**  **to be prepared for each set of reagents.**

5. Comment: **Commenter #7 commented, regarding Method 8000D (Sec tion 9.3): Section 9.3.4.4: Multiple**  **laboratory performance data are included in some de terminative methods and may be used as**  **guidance in evaluating performance in a single labo ratory. Many of the individual organics**  **methods in SW-846 do not have acceptance criteria s o default limits should be defined. We**  **suggest adding the target limits 50% to 150% for re covery.** 

Response: **The following language was added to Section 9.3.4.4 : "Once sufficient data points are available,**  **each laboratory is strongly encouraged to develop i n-house control limits." DoD 2013 LCS**  **study results can be referenced in Section 16 of Me thod 8000D.** 

6. Comment: **Commenter #7 commented, regarding Method 8000D (Sec tion 9.7): The laboratory shall**  **establish the LLOQ as the lowest point of quantitat ion, which in most cases, is the lowest** 

**concentration in the calibration curve. It would b e helpful to include a more complete and** 

**detailed section in Method 8000D that describes tec hniques to establish the LLOQ. Simply**  **defining it as the lowest concentration in the cali bration curve does not seem adequate or**  **appropriate in many cases. There are situations wh ere you would want to have calibration**  **standards below the equivalent LLOQ for a particula r sample matrix to establish more**  **appropriate calibration factors near the LLOQ. We would recommend referencing the following**  **approach for determining the LLOQ, to be done as pa rt of the method validation process:**  **Report of the Federal Advisory Committee on Detecti on and Quantitation Approaches and Uses**  **in Clean Water Act Programs (December 2007).**

Response: **The Agency thanks the commenter for their input. T he language in Section 9.7 has**  **been updated. Page 33** 

7. Comment: **Commenter #7 commented, regarding Method 8000D, tha t acceptance criteria for linear**  **regressions (Section 11.5.2.2): r or r 2**  **should be at or above 0.995 and 0.99, respectively . I** 

**think this should remain as a "must" criterion.**

Response: **The Agency will retain the existing language in the method. The use of "should" in the text is to**  **allow flexibility for project-level DQOs to determi ne the data use.** 

8. Comment: **Commenter #9 commented, regarding Method 8000D (fou nd on FR Page 63192), that they**  **approve of basing the LLOQ acceptance limits on the laboratory control sample limits with the**  **addition of 20 percent.**

Response: **The Agency appreciates the input.**

9. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 9.4.2.1, and Method 6010D,**  **Section 9.7.2, that the "1 - 5 times the background concentration" is not always appropriate. If**  **the background concentration is very low or non-det ect (e.g., organic analytes), any spike**  **amount may lead to a ratio between the spike concen tration and the background concentration**  **> 5; however, the MS/MSD data are generally useable . Recommended edit: Suggest that a**  **NOTE such as "NOTE: If the background sample concen tration is very low or non-detect, a**  **spike of greater than 5 times the background concen tration is still acceptable. To assess data**  **precision with duplicate analyses, it is preferable to use a low concentration field sample to**  **prepare MS/MSD for organic analyses and a high conc entration field sample to prepare**  **unspiked laboratory duplicates for metals analyses. "** 

Response: **The Agency agrees and has added the following note to Section 9.4.2.1 of Method 8000D:**  **"NOTE: If the background sample concentration is v ery low or non-detect, a spike of greater**  **than 5 times the background concentration is still acceptable. To assess data precision with**  **duplicate analyses, it is preferable to use a low c oncentration field sample to prepare a MS/MSD**  **for organic analyses."**

**The following note was added to Section 9.7.2 of 60 10D and 6020B: "NOTE: If the background**  **sample concentration is very low or non-detect, a s pike of greater than 5 times the background**  **concentration is still acceptable. To assess data precision with duplicate analyses, it is**  **preferable to use a high concentration field sample to prepare unspiked laboratory duplicates for**  **metals analyses."**

10. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 11.5.2.2, that the first sentence**  **of the last paragraph, "In order for the linear reg ression model to be used for quantitative** 

**purposes, r or r 2**  **should be ≥ 0.995, and 0.99, respectively" needs a revision. Recommended**  **edit: Change the sentence to "In order for the line ar regression model to be used for quantitative** 

**purposes, r or r 2**  **should be ≥ 0.995 or 0.99, respectively."**

Response: **The Agency agrees and made the requested edit. Page 34** 

11. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 11.5.4.2: "If the RSD limit is not**  **defined in the determinative method, the limit shou ld be set at ≤20% for good performing**  **compounds and ≤30% for poor performing compounds." Poor performing compounds are**  **laboratory dependent, and should be held to same cr iteria as other analytes unless removed**  **from consideration through the DQO process. Recomm ended edit: Remove the 30% criteria for**  **poor performers.**

Response: **The Agency disagrees with the commenter and Section 11.5.4.2 remains unchanged.** 

12. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 11.5.6.1, that RSE should not be**  **grouped with RSD and r 2**  **, but with % Error. Standard deviation (SD) and r 2**  **are indicators for checking the validity of different calibration meth**  **ods of response factor and least square linear regression techniques, respectively. RSE is not eq**  **uivalent or similar to RSD or r 2**  **, but similar to % Error and may be used to back check a calibration**  **curve. To avoid confusions with RSD, RSE should not be grouped with RSD; especially sinc**  **e there is no mathematical derivation for RSE like RSD. Recommended edit: Change the first s**  **entence to "Corrective action may be needed if the calibration criteria (RSD/r**  **2 and % Error/RSE) are not met."** 

Response: **The Agency agrees with the commenter and made the e dit in the text.** 

13. Comment: **Commenter #4 suggested, regarding Method 8000D, Sec tion 11.8.2, that a closing CCV be run**  **at the end of a run sequence for both external and internal standard calibrations. The validity of**  **a calibration curve should be checked, despite the type of calibration techniques.**  **Recommended edit: Change the second to the last sen tence to "All samples analyzed should**  **be bracketed with a continuing calibration verifica tion (CCV) standard at the beginning and the**  **end of the analytical sequence."**

Response: **The Agency disagrees with the commenter. Section 1 1.8.2 remains unchanged.** 

14. Comment: **Commenter #4 recommended, regarding Method 8000D, S ection 16: Add an additional DoD**  **reference document, QSM Version 5.0, which contains updated LCS control limits. Do not**  **delete DoD QSM Version 4.2, which has a list of poo rly-performing compounds. Recommended**  **edit: Add "Department of Defense: "Quality Systems Manual for Environmental Laboratories",**  **Version 5.0 http://www.denix.osd.mil/edqw/upload/QS M-Version-5-0-FINAL.pdf."** 

Response: **The Agency agrees and the additional reference was added to Method 8000D in Section 16.** 

15. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 9.2.1, that it is generally**  **advisable, although not required, that all method Q C samples be run at the same time as the**  **samples on the same instrument. This should be req uired, not advisable. Recommended edit:** 

**Delete the sentence. Page 35** 

Response: **The Agency thanks the commenter for their input, bu t disagrees with the proposed edit. The**  **existing text has been retained.**

16. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 9.2.6.2, that when samples that**  **are extracted together are analyzed on separate ins truments or in separate analytical shifts, the**  **method blank associated with those samples (e.g., e xtracted with the samples) must be**  **analyzed on at least one of those instruments. Rec ommended edit: "When samples that are**  **extracted together are analyzed on separate instrum ents or in separate analytical shifts, the**  **method blank associated with those samples (e.g., e xtracted with the samples) must be**  **analyzed on each of those instruments".**

Response: **The Agency thanks the commenter for their input, bu t disagrees with the proposed edit. The**  **existing text has been retained.**

17. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 9.4.2, that for those methods**  **that apply to a large list of analytes or that cont ain compounds that may interfere with an**  **accurate assessment (i.e., coeluting or multi-peak analytes), a smaller subset of analytes may**  **be used. All analytes that are reported to a clien t should be included in the LCS/MS/MSD.**  **Recommended edit: All analytes that are reported to a client should be included in the** 

**LCS/MS/MSD.**

Response: **The Agency thanks the commenter for their input. T hat specification can be included in a**  **project QAPP if needed, but will not be required in Method 8000D. Laboratories often include**  **samples received from multiple clients in an analyt ical batch. Analytical requirements including**  **but not limited to compound lists will vary by clie nt/project and the LCS/MS/MSD for a client/**  **project-specific target analyte list is not necessa rily the same as the one for another client or**  **project. Therefore, no change has been made based on the comment.** 

18. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 9.7, that the first sentence of the**  **first paragraph, "The laboratory shall establish th e LLOQ as the lowest point of quantitation,**  **which in most cases, is the lowest concentration in the calibration curve", may be misleading.** 

**The lowest calibration standard does not establish an LLOQ either but it shall be equal to or less**  **than the LLOQ to support the LLOQ (i.e., an LLOQ mu st be within a calibration range for**  **reliable quantitation). The first sentence is not clear and should be revised. Recommended**  **edit: Change the first sentence to, "The laboratory shall establish its LLOQ as the lowest point of**  **quantitation, which shall be within the instrument calibration range. An LLOQ could be equal to** 

**the lowest calibration standard if the associated d ata precision and bias at the LLOQ are known** 

**and documented."**

Response: **The Agency appreciates the feedback. This change w as discussed in the work group and the**  **first lines of Section 9.7 were updated to the foll owing: "The LLOQ is the lowest concentration at**  **which the laboratory has demonstrated target analyt es can be reliably measured and reported**  **with a certain degree of confidence, which must be ≥ lowest point in the calibration curve. The** **Page 36**

**laboratory shall establish the LLOQ at concentratio ns where both quantitative and qualitative**  **requirements can consistently be met (see Sections 9.9 and 11.6)."** 

19. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 9.7, that the last sentence of the**  **first paragraph, "Optimally, the LLOQ should be les s than the desired regulatory action levels**  **based on the stated DQOs", is not sufficient. EPA needs to provide procedures and/or**  **guidance on how to determine the "less" quantitativ ely. This Section describes many excellent**  **concepts and recommendations but lacks detailed pro cedures for performing them. Without**  **procedures, this sentence is troublesome and not ve ry useful. Recommended edit: Suggest**  **that EPA provide procedures and/or guidance for est ablishing quantitative data quality**  **requirements on precision, bias, and sensitivity ba sed on project DQOs. It is not appropriate to**  **state that this is a project DQO or planning proces s.** 

Response: **The Agency thanks the commenter for their input, bu t disagrees that a change is needed. The**  **Agency does not currently publish a procedure for d etermining what the level of the LLOQ (or its**  **associated check standard) standard should be. The current practice is to use the bottom point** 

**of the calibration curve for the determinative meth od.** 

20. Comment: **Commenter #4 commented, regarding Method 8000D, Sec tion 9.7, that "LLOQ verification is**  **recommended for each project application to validat e quantitation capability at low analyte** 

**concentration levels." Recommended edit: The minim um frequency required to verify the LLOQ**  **(such as per batch) should be defined.**

Response: **Frequently performed analyses, such as Methods 8260 C and 8270D, should have a LLOQ**  **check standard verified, at minimum, once a year. This language was added to Method 8000D** 

**in Section 9.7.2.**

Comments received on Method 8000D after the public comment period had ended:

Comment #1a **, per the MICE Line, 8000D requirements apply to al l previous versions of**  **methods. It supersedes 8000C, B, etc. Is this cor rect and does this logic also apply to the**  **updated Chapters?**

Response: **The Agency thanks the commenter for the question; h owever, the Agency feels the response to**  **the original MICE inquiry may be misinterpreted. H ere is the MICE response:** 

**“As stated in Section 1.1, Method 8000 is not a det erminative method but instead provides**  **guidance on analytical chromatography and describes calibration and QC requirements**  **common to all SW-846 chromatographic methods. Howe ver, more specific QC requirements**  **provided in the applicable determinative method wil l supersede those noted in Method 8000.**  **Method 8000 should be applied in conjunction with a ll SW-846 determinative chromatographic**  **methods. Method 8000D (the current version in Upda te V) is a general guidance method for**  **organics. As such it includes the most up to date guidance (including revised initial**  **demonstration of proficiency (IDP), lower level of quantitation (LLOQ) and relative standard**  **error (RSE)) on general chromatography in SW-846. The determinative methods are more**  **specific in their requirements for particular analy ses (such as 8260B for volatiles) and the** **Page 37**

**determinative method's criteria supersede any gener al guidance found in 8000D or Chapter 1, if**  **specific conflicts exist. Method 8260 has an updat ed version, 8260C, which is available at:**  **http://www.epa.gov/epawaste/hazard/testmethods/pdfs /8260c.pdf.** 

**The older, published methods (such as 8260B and 800 0C) are still valid choices and may still**  **be followed by those with a need to do so. We reco mmend using the newest version of any**  **SW-846 method, unless your regulator or customer re quires you to use an earlier version.”** 

Comment #1b

**, LLOQ – prepped spike at the LOQ; for Organics under**  **8000D Section 9.2.1, this standard must be analyzed every 12 hours. Thi**  **s requirement adds QC to the analytical run which takes away a sample analysis. This will incr**  **ease cost to the lab in both preparation and analytical time as well as the cost of the standard**  **itself and the associated solvents. We would suggest that the frequency be changed to analysis p**  **er ICAL.**

Response: **The Agency agrees with the commenter and has remove d the LLOQ requirement from Method**  **8000D, Section 9.2.1.**

Comment #1c **, the method states to spike the LLOQ at the LOQ. We suggest an allowance for**  **using a spiking range (<LOQ to 4 X LOQ). To spike at the LOQ would either cause the need to**  **analyze multiple standards to encompass the levels or to potentially raise LOQs to match a** 

**standard.**

Response: **The Agency appreciates the feedback. The work grou p discussed this topic and the following**  **language was added to Section 9.7.2: "The LLOQ veri fication (to be performed after the initial**  **calibration) is prepared by spiking a clean control material with the analyte(s) of interest at 0.5 -**  **2 times the LLOQ concentration level(s). Alternati vely, a representative sample matrix free of**  **targets may be spiked with the analytes of interest at 0.5 - 2 times the LLOQ concentration** 

**levels."**

Comment #1d **, Inorganics already has the LLOQ requirement under Update IV. With the**  **acceptance criteria that need to be met for this st andard, the LOQs needed to be raised 2-fold**  **under Update IV. This is the same for Update V.**

Response: **The Agency appreciates the feedback. The work grou p discussed the LLOQ language and has**  **updated Section 9.7. Page 38**  METHOD 8021B

1. Comment: **(The Agency received two comments on the same topic for this method. The**  **response covers both.)**

**Commenter #3 commented, regarding Methods 8021B, 81 11, 8270D, 8410, that confusion over**  **the appropriate naming convention for bis(2-chloro- 1-methylethyl)ether has been a thorny issue**  **for years and we appreciate the clarification provi ded in this update.** 

**and**

**Commenter #9 commented, regarding Methods 8021B, 81 11, 8270D, 8410, FR page 63191:**  **thanks and congratulates the Agency on the resoluti on of the bis(2-chloro-1-methylethyl)ether**  **naming issue (as requested by the commenter).**

Response:

**The Agency thanks the commenters for their input an d is gratified that the clarification provided**  **was helpful to the method users. Page 39**  METHOD 8111

1. Comment: **(The Agency received two comments on the same topic for this method. The**  **response covers both.)**

**Commenter #3 commented, regarding Methods 8021B, 81 11, 8270D, 8410, that confusion over**  **the appropriate naming convention for bis(2-chloro- 1-methylethyl)ether has been a thorny issue**  **for years and we appreciate the clarification provi ded in this update.** 

**and**

**Commenter #9 commented, regarding Methods 8021B, 81 11, 8270D, 8410, FR page 63191:**  **thanks and congratulates the Agency on the resoluti on of the bis(2-chloro-1-methylethyl)ether**  **naming issue (as requested by the commenter).**

Response:

**The Agency thanks the commenters for their input an d is gratified that the clarification provided**  **was helpful to the method users. Page 40**  METHOD 8270D

1. Comment: **(The Agency received two comments on the same topic for this method. The**  **response covers both.)**

**Commenter #3 commented, regarding Methods 8021B, 81 11, 8270D, 8410, that confusion over**  **the appropriate naming convention for bis(2-chloro- 1-methylethyl)ether has been a thorny issue**  **for years and we appreciate the clarification provi ded in this update.** 

**and**

**Commenter #9 commented, regarding Methods 8021B, 81 11, 8270D, 8410, FR page 63191:**  **thanks and congratulates the Agency on the resoluti on of the bis(2-chloro-1-methylethyl)ether**  **naming issue (as requested by the commenter).**

Response:

**The Agency thanks the commenters for their input an d is gratified that the clarification provided**  **was helpful to the method users.**

2. Comment: **Commenter #4 commented, regarding Method 8270D, Sec tion 11.3.6.3, that "If compounds fail**  **to meet these criteria, the associated concentratio ns may still be determined but they must be**  **reported as estimated." This statement appears to allow analytes that fail calibration to be**  **reported as estimates. Analytes that fail calibrat ion should not be reported. Recommended**  **edit: This statement appears to allow analytes that fail calibration to be reported as estimates.**  **Analytes that fail calibration should not be report ed.** 

Response: **The Agency thanks the commenter for their input. T his comment is valid and this subject will be**  **addressed in Method 8270E, which will be released i n Update VI.** **Page 41** METHOD 8290

1. Comment: **Commenter #8 commented that the response detailed b elow provides an alternative to the**  **LLOQ concept published in the above-referenced noti ce regarding an update to SW-486,**  **particularly for isotope dilution methods, such as Method 8290. Additionally, the response**  **explains both why this approach represents a desira ble extension to the LLOQ concept and**  **addresses some questions regarding the underlying r ationale behind the LLOQ. To be clear,**  **SGS approves whole-heartedly of ORCR's decision to remove references to the MDL, for all of**  **the reasons that ORCR stated for doing so and many others. SGS also approves of ORCR's**  **embrace of EPA's Flexible Approach. SGS supports t he aim of the Flexible Approach to permit**  **quicker and easier adoption of advancing technology without the time lag inherent in**  **promulgation of new methods by the Agency.**

**The alternative offered here (commenter submitted a paper in support) is in accord with ORCR's**  **obvious interest in improving the quality and inter pretation of analytical data. SGS believes that**  **this alternative extends upon the concepts underlyi ng the LLOQ, in general, rather than**  **negating them. SGS applauds ORCR's clear desire to improve analytical data and offers this**  **alternative in that same spirit.**

Response: **The Agency thanks the commenter for their input. I sotope dilution methods, such as 8290, are**  **not in the scope of Update V. An alternative to th e LLOQ in a paper provided by SGS will be** 

**considered when we re-evaluate Method 8290 or other isotope dilution methods.** **Page 42** METHOD 8410

1. Comment: **(The Agency received two comments on the same topic for this method. The**  **response covers both.)**

**Commenter #3 commented, regarding Methods 8021B, 81 11, 8270D, 8410, that confusion over**  **the appropriate naming convention for bis(2-chloro- 1-methylethyl)ether has been a thorny issue**  **for years and we appreciate the clarification provi ded in this update.** 

**and**

**Commenter #9 commented, regarding Methods 8021B, 81 11, 8270D, 8410, FR page 63191:**  **thanks and congratulates the Agency on the resoluti on of the bis(2-chloro-1-methylethyl)ether**  **naming issue (as requested by the commenter).**

Response:

**The Agency thanks the commenters for their input an d is gratified that the clarification provided**  **was helpful to the method users.**

2. Comment: **Commenter #4 commented, regarding Method 3200, Sect ion 11.2.1.4, that the section states**  **cold sample storage requirements "Store extracts in the cold at 4**  ° **C until analysis". The current storage requirements as stated in Chapter 3 are to**  **"store extracts in the cold at ≤6** ° **C until analysis." Recommended edit: Update from old requi**  **rements (4** ° **C) to new requirements (≤6**

° **C).**

Response: **The Agency agrees with the commenter and has made t he requested change in Method 3200,** 

**Section 11.2.1.4.**

**The rest of the Update V methods were searched and the same temperature range correction**  **was made in Method 8410 (Section 7.4.2) and Method 8430 (Sections 7.5.2, 8.2 and 11.3.4).** **Page 43** METHOD 8430

1. Comment: **Commenter #4 commented, regarding Method 3200, Sect ion 11.2.1.4, that the section states**  **cold sample storage requirements "Store extracts in the cold at 4**  ° **C until analysis". The current storage requirements as stated in Chapter 3 are to**  **"store extracts in the cold at ≤6** ° **C until analysis." Recommended edit: Update from old requi**  **rements (4** ° **C) to new requirements (≤6**

° **C).**

Response: **The Agency agrees with the commenter and has made t he requested change in Method 3200,** 

**Section 11.2.1.4.**

**The rest of the Update V methods were searched and the same temperature range correction**  **was made in Method 8410 (Section 7.4.2) and Method 8430 (Sections 7.5.2, 8.2 and 11.3.4).** **Page 44** METHOD 9014

1. Comment: **Commenter #4 commented, regarding Method 9014, that Section 10.1 and 10.2 detail the**  **concentrations of the calibration standards, and th at the calibration curve is generated by**  **plotting absorbance versus concentration, but does not include or reference any acceptance**  **criteria for the curve, such as correlation coeffic ient or coefficient of determination.**  **Recommended edit: Add sections specifying the accep tance criteria for calibration curves when**  **employing the colorimetric options in this method.**

Response:

**The Agency thanks the commenter for their input. D etailed information on calibration models**  **and their acceptance criteria is not included in ea ch SW-846 method. The methods are**  **intended as general guidance. For any test methods which are not method-defined parameters**  **(MDPs), the intention is to allow the laboratory fl exibility under the Methods Innovation Rule**  **(MIR). The details of how a laboratory will conduc t and approve calibrations should be included**  **in the individual laboratory's QMP and in their SOP s for each method. SW-846 method limits**  **are not intended to be mandatory QC acceptance crit eria.** **Page 45** METHOD 9040

1. Comment: **Commenter #1 commented, regarding Method 9040, that Method 9040, which is specified in 40**  **CFR 261.22(a)(1) as the analytical method to be use d for establishing the pH of an aqueous**  **waste, states that this "method is used to measure the pH of aqueous wastes and those**  **multiphase wastes where the aqueous phase constitut es at least 20% of the total volume of the** 

**waste."**

**This statement in 9040 is being used by the regulat ed community to assert, for example, that a**  **55-gallon drum full of strong sodium hydroxide liqu id and steel pieces is not a D002 hazardous**  **waste if the volume of liquid is less than 11 gallo ns (55 x 0.20 = 11). Such a waste would phase**  **separate, with the sodium hydroxide liquid on top a t a depth of up to 6 inches (6 inches is 20%**  **of 30 inches, the approximate height of a 55-gal dr um). Clearly a pH could be easily obtained**  **with 6 inches of depth to insert a pH meter's probe into, and hence such a drum-full of waste**  **should clearly be classified as a D002.**

**This statement in method 9040 should be changed in Update V to make it clear that, depending**  **on the sample, 9040 may still be suitable for D002 determinations even if the aqueous phase** 

**constitutes less than 20% of the entire waste. Inc identally, at least one EPA guidance**  **document, RO# 11738, erroneously concludes from the above sentence in 9040 that "any**  **waste for which [9040] is applicable must contain a t least 20% free water by volume."** 

Response: **The Agency thanks the commenter for their input. M ethod 9040 is a method-defined parameter**  **(MDP) and as such would have to be revised by a for mal rulemaking. Method 9040 is not**  **included in Update V and as such, is not subject to revision at this time. The Agency will retain** 

**the comment to be discussed the next time Method 90 40 is updated.** **Page 46** REFERENCE TABLE

1. Comment: **Commenter #1 commented, regarding the Reference Tab le, that one of the documents in the**  **Docket (i.e., EPA-HQ-RCRA-2012-0072-0023) has a fau lty link for the following entry: "USEPA.**  **Waste Analysis at Facilities That Generate, Treat, Store and Dispose of Hazardous Wastes,**  **ECDIC 2002-011. Office of Waste Programs Enforceme nt, United States Environmental**  **Protection Agency. April 1994". The faulty link is :**  **http://www.epa.gov/compliance/resources/policies/ci vil/rcra/wasteanalygman-rpt.pdf.**  **This link produces an error message. This "waste a nalysis" document – which is the April 1994**  **version and not the draft January 2013 version – is believed to instead be at:**  **http://www.epa.gov/osw/hazard/tsd/ldr/wap330.pdf. Readers attempting to use the faulty link may, afte**  **r receiving the error message that this link does not exist, do a "Google search" for this docum**  **ent and are likely to select the January 2013 version of this document. However, the January 201**  **3 version is only a draft (and was reported in comments to have a number of errors).** 

Response: **The Agency agrees with the commenter that the displ ayed link is not functioning at this time. A**  **link to the 2013 guidance can be found at: http://w ww.epa.gov/epawaste/hazard/tsd/permit/tsd**  **regs/tsdf-wap-guide.pdf. Page 47**  GENERAL COMMENTS

1. Comment: **Commenter #3 commented that they welcomed the oppor tunity to comment on Update V to**  **SW-846. They believe this update considerably stre ngthens and clarifies the guidance**  **provided, and appreciate the work the agency contin ues to put into improving the manual.**  **The clarifications to status of methods and especia lly the strong guidance to prefer the latest**  **version of a method are useful and should improve t he consistency with which methods are**  **selected by the data users and generators.**

Response: **The Agency thanks the commenter for their input and is gratified that the clarification provided**  **was helpful to the method users.**

2. Comment: **Commenter #9 commented regarding FR Pages 63187 and 63188: The commenter thanks and**  **congratulates the Agency on the clarifications to t he status of SW-846 methods, naming**  **conventions and the strong statement regarding pref erence for using the latest method version**  **(as previously requested by commenter).**

Response: **The Agency thanks the commenter for their input and is gratified that the clarification provided**  **was helpful to the method users.**

3. Comment: **Commenter #9 commented regarding FR Pages 63191 and 63192: The commenter approves of**  **the addition of a formal quantitation limit termed the LLOQ.** 

Response: **The Agency thanks the commenter for their input.**

4. Comment: **Commenter #9 commented regarding FR Pages 63191 and 63192: The commenter recognizes**  **that the current MDL procedure does not meet ORCR n eeds, but the commenter believes that**  **the Office of Water is considering an update to the MDL, in which case ORCR may want to**  **reconsider its position at some time in the future because the LLOQ would be more effective in** 

**combination with a reliable detection limit.**

Response: **The Agency thanks the commenter for their input and will review any new policies published for**  **relevance and possible use by ORCR in future update s.** 

5. Comment: **Commenter #9 commented regarding FR Page 63191: Reg arding the elimination of the use of**  **the current MDL, the commenter agrees with ORCR tha t the MDL in its current form has no**  **place in the program. However, should The NELAC In stitute's proposed revisions to the MDL**  **be accepted, the MDL could be valuable for making t he determination that a waste is**  **nonhazardous for a given constituent if that consti tuent is not detected and the MDL is less than**  **the RCRA limit. The only caveat is that it is nece ssary to be certain that the MDL is appropriate**  **for the specific matrix to which it is being applie d. This may mean that the generator would** 

**have to demonstrate that the MDL can be verified in its specific matrix.** **Page 48**

Response: **The Agency thanks the commenter for their input and will review any new published standards**  **for relevance and possible use by ORCR in future up dates.** 

6. Comment: **Commenter #9 commented regarding FR Page 63192: The commenter approves of the**  **changes to the Initial Demonstration of Proficiency requirements.** 

Response: **The Agency thanks the commenter for their input.**

7. Comment: **Commenter #9 commented (FR Pages 63192 and 63193): The commenter approves of the** 

**addition of the relative standard error as a method for evaluation of calibration curves and**  **appreciates the consistency with similar approval i n 40 CFR Part 136.** 

Response: **The Agency thanks the commenter for their input.**

8. Comment: **Commenter #4 commented that the chapters refer to t he methods for details and guidance on**  **establishing and verifying the LLOQs, but little gu idance can be found in the methods.**  **Recommended edit: Clarify details on establishing a nd verifying the LLOQs, and clarify the**  **location of the guidance both within the chapters a nd the methods.** 

Response:
**Guidance on LLOQ verifications can be found in Meth ods 6010D and 6020B (Section 9.8 for**  **both) for inorganics as well as Method 8000D (Secti on 9.7) for organics.** 

9. Comment: **Commenter #4 commented that the LLOQ requires quart erly verification, but it is unclear exactly**  **how the verification is performed. Recommended edi t: Clearly define how the LLOQ verification**  **should be performed.**

Response: **The determinative methods may specify how often a p articular method's LLOQ verification**  **should be performed. For inorganic methods (such a s 6010B and 6020B) the requirement is a**  **minimum of quarterly. For organic methods, 8000D s pecifies the following in Section 9.7.2: "It is**  **recommended to analyze the LLOQ verification on eve ry instrument where data is reported;**  **however, at a minimum, the lab should rotate the ve rification among similar analytical**  **instruments such that all are included within 3 yea rs. Frequently performed analyses, such as**  **Methods 8260C and 8270D, should have an LLOQ check standard be verified, at minimum,**  **once a year."**

10. Comment: **Commenter #4 commented that the guidance is unclear on the topic of how many different** 
**matrices the LLOQ should be determined for and how to mimic the matrix in the LLOQ**  **determination. Clarify how the laboratory should m imic the matrix for the LLOQ determination.** **Page 49**

Response: **LLOQ can be determined using either clean control m aterial (e.g., reagent water, solvent blank,**  **Ottawa sand, diatomaceous earth, etc.) or a represe ntative sample matrix, free of target**  **compounds. Optimally, the LLOQ should be less than the desired regulatory action levels**  **based on the stated DQOs. For a specific project w ith established DQOs, a representative**  **sample, free of target compounds, may be used to pr ovide a more reliable estimate of the lower**  **quantitation limit capabilities. For more informat ion, please see Section 9 of Method 8000D.** 

11. Comment: **Commenter #4 commented that no guidance is presente d on spiking level. It states the LLOQ**  **should be the lowest calibration concentration, but spiking at that level with recoveries less than**  **100% would require calculating data below the curve which is not acceptable now unless**  **qualified. So should the spike level be 35% higher than the lower calibration standard? This**  **way any result below the lowest calibration standar d would be not acceptable. Also they refer to**  **making sure the LLOQ is below the regulatory limits . These limits for the samples the lab**  **receives are not usually known and also vary by sta te etc. Insert guidance on the spiking** 
**concentrations for LLOQs.**

Response: **The Agency thanks the commenter for their input. T he LLOQ is prepared by spiking the**  **analyte(s) of interest at 0.5 - 2 times the LLOQ co ncentration level(s) per Method 8000D and <2**  **times the LLOQ for inorganic methods. The LLOQ che ck is carried through the same**  **preparation procedures as environmental samples and other QC samples. Recovery of target**  **analytes in the LLOQ verification should be within established in-house limits, or other such**  **project-specific acceptance limits, to demonstrate acceptable method performance at the LLOQ.**  **The laboratory would need to verify with data user( s) and/or regulatory authority to ensure**  **project DQOs (including RLs) are appropriate prior to conducting the analysis.** 

12. Comment: (The Agency received several comments regarding LLOQ and MDL. They are combined for the response.)

**Commenter #4 commented that various environmental a pplications (risk assessment, statistical**  **evaluations, etc.) that utilize SW-846 methods rely heavily on the use of "detected" data.** 

**Elimination of the MDL without further clarificatio n on issues regarding reporting and use of data**  **below the LLOQ will lead to confusion. Further gui dance is needed. Recommended edit:**  **Clarify how to report and use data below the LLOQ.**

**and**

**Commenter #5 commented that the proposed change to SW-846 that would eliminate the MDL**  **and substitute a new parameter called the LLOQ. Th is change removes information from the**  **test report that is very helpful to state environme ntal agencies responsible for evaluating and**  **remediating public health risks associated with haz ardous substance discharges. Currently,** 

**detections below the RL and above the MDL are state d and qualified with a J flag. This means**  **that the chemical is in the sample but can't be qua ntified well enough to make the quantity** 

**measurement usable. However there is a 90% certain ty that the chemical is in the sample. It is**  **very important to know if a specific chemical is in the sample, even though one doesn't know** 

**how much there is. The reasons are several:**

**1. Some health standards are below RLs. If it is r eported with a J flag that a chemical of** 

**concern with a health standard below the RL is in t he sample then the professional evaluating**  **the contamination site knows that there is a potent ial health impact that must be searched out** **Page 50**

**by some other means of investigation. If the chemi cal of concern is present at concentrations**  **lower than the LLOQ, then it would go unnoticed und er this proposed change to the method,**  **leaving the possibility that the health of people l iving on or near this site may be threatened.** 

**2. In most cases the health standard is above a RL. In these instances it is also helpful to have**  **a chemical of concern J flagged. For example, if t he substance is the target of a monitoring**  **system and it has been identified by a J flag, reme diation professionals would continue**  **monitoring for the chemical to see if it will incre ase to the point where it may exceed the health**  **standard. If this change in the method were adopte d the professionals would not see the**  **chemical of concern reported and would discontinue monitoring for this chemical. This could**  **cause them to miss the potential situation where, w ith time, it increased in value above the**  **health standard. This mistake could put someone's health at risk that might be living at or near** 

**the site.**

**and**

**Commenter #6 commented that according to update V, both the MDL procedure and the LLOQ**  **procedure may be performed using a clean matrix or control material. It is our opinion that the**  **LLOQ procedure is not more representative of comple x matrices. We understand that the**  **LLOQ procedure may be performed using a representat ive sample matrix free of target**  **compounds, but given the option it is likely that t he laboratories will opt to use a clean control**  **material (e.g., reagent water, method blanks, Ottaw a sand, diatomaceous earth, etc.).**  **The quotes below taken directly from the Federal Re gister notice of availability support our**  **opinion: The procedure outlined in Part 136 is generally not**  **suitable for RCRA wastes or materials because the MDL approach generally yields unrealist**  **ic and/or unachievable method detection limits for the complex matrices (e.g., soils, sludg**  **es, wipes, and spent materials) encountered under the RCRA program. The MDLs are normally calc**  **ulated from analysis of a sample that does not cause matrix interferences (typically dete**  **rmined using spiked reagent water). Establishing LLOQ for Inorganic analytes: When perf**  **orming methods for inorganic analyses, the LLOQ should be verified by the analysis of at least**  **seven replicate samples (prepared in a clean matrix or control material) and spiked at the LLOQ**  **and processed through all preparation and analysis steps of the method.**  **This verification may be accomplished either with c lean control material (e.g., reagent water,**  **method blanks, Ottawa sand, diatomaceous earth, etc .) or a representative sample matrix free**  **of target compounds. Establishing LLOQ for organic analytes: When perfor**  **ming methods for organic analyses, the LLOQ should be verified using either a clean contro**  **l material (e.g., reagent water, method blanks, Ottawa sand, diatomaceous earth, etc.) or a**  **representative sample matrix free of target compounds.** 

Response: **ORCR understands that other EPA programs may contin ue to use MDLs to meet their program**  **use and needs (e.g., the National Pollutant Dischar ge Elimination System (NPDES) permit**  **program). However, ORCR has found that the procedu re in 40 CFR 136, Appendix B, for the**  **determination of MDLs, developed for the Clean Wate r Act (CWA) program, uses a clean matrix**  **(e.g., reagent water for preparing "spiked" samples , or samples with known constituent**  **concentrations). Analytical laboratories often hav e difficulty demonstrating they can meet the**  **MDL established using Part 136 when evaluating comp lex matrices, such as wastes. The**  **procedure outlined in Part 136 is generally not sui table for RCRA wastes or materials because**  **the MDL approach generally yields unrealistic and/o r unachievable MDLs for the complex** **Page 51**

**matrices (e.g., soils, sludges, wipes, and spent ma terials) encountered under the RCRA**  **program. The MDLs are normally calculated from ana lysis of a sample that does not cause**  **matrix interferences (typically determined using sp iked reagent water). However, most wastes**  **evaluated for compliance with RCRA consist of compl ex matrices. The LLOQ considers the**  **effect of sample matrix (e.g., components of a samp le other than the analyte) by taking the**  **sample through the entire analytical process, inclu ding sample preparation, clean up (to remove**  **sample interferences), and determinative procedures . If a laboratory has a need to report a**  **value that is at or above the MDL, but lower than t he LLOQ, it may do so with qualification, such**  **as a flag of "J" to represent that the value is a q ualitative positive hit but is not considered to be**  **quantitatively accurate. Other forms of qualificat ions may also be used as long as they meet the**  **projects DQO and/or any other regulatory requiremen ts.**