# Instructions for Using EP A Spreadsheet to Submit Solvent Y ellow 124 T est Method Precision and Accuracy Information

Transportation and Regional Programs Division Office of Transportation and Air Quality U.S. Environmental Protection Agency

May 2007 (Minor Revisions January 22, 2009)

OMB Control Number: 2060-0308 Expiration Date: December 31, 2011

EPA-420-B-09-004 February 2009Disclaimer

The discus s ion in this document is intended solely as instructi ons. The statutory provisions and EPA re gulatio ns described h e re contain legally bin d ing requir ements. This document is not a regulation itself, nor does it change or substitute for those provisions and regulat ions. Thus it does not impose legally binding requirements on EPA, States, or the regulated co mmunity. These instructions do not confer l egal rights or impose legal obligat ions upon any member of the public.

While we have made every effort to ensur e the accuracy of the discussion in these instructions, the obligations of the regul ated community are determi ned by statutes, regulations , or other legally binding requirement s. In the event of a conflict between the discussion in this document and any statute orregulation, this document would not be controllin g.
The general description of the applicati on process provided here may not apply to a particular situation. Interested parties are fr ee to raise questions about the substance of these instructions and its applica b ility to a particular situation. EPA may adopt approaches on a case-by-case basis that differ from those described in these instructions.

Mention of trade names or co mmercial products does not constitute endorsement or recommendation for their use.

The sampling, sample preparation, and testi ng methods qualified for use in accordance with the requirements of sect ion 40 CFR § 80.582 may involv e the use of hazardous materials, operations and equipm ent. These instructions do not address the associated safety problems which may exis t. It is the responsibility ofthe user of the procedures specified in these instructions to establis h appropriate safety and health practices prior to their use. It is also the respons ibility of the user to dispose of any byproducts which might result from conducting these procedur es in a manner consis tent with applicable safety and health requirements.

This is a liv ing docum ent and may be revised periodica lly without public notic e

. EPA welcomes public input on this document at any time.

iIntroduction: On May, 2004, EPA promulgated new requiremen t s for non-road diese l fuel. One of the provi s ions of this final rule, explained in Subpart I of 40 CFR Part 80, requires that each test facility must meet specified acc u racy and precision cr iteria with its chosen test method for the fuel marker solvent yellow 124 in heating oil and non-road locomotive and marine diesel fuels. Evi dence of having met these requirements must be submitted to and approved bythe Agen cy before using the method to make measurements for demonstrating compliance. The fol l owing instructions are for use by those parties that need to qualify a facility/te st method for measuring the concentration of this marker in heating oil or non-road lo comotive and marine diesel fuel pursuant to 40 CFR 80. 510. 1

EPA has pr ovided a sp readsheet template for recording and evalu a t ing the test data required for establishing the test method’s pr ecision and accuracy. Use of the template will, we ho pe, help an applica n t to struct ure and submit the needed information. It will also facilitate EPA’s timely review and appr oval of test methods. Part I belo w exp l a i ns the use of the template, while Part II cove rs submission of t he resulting structured information to EPA.

Part I - Instructions for use of spr eadsheet for evaluating method precision and accuracy.

I. Precision demonstration for solvent y e llow124 test method.

Precision Criterion 2 - a standard deviatio n le ss t han 0.10 milligram s per liter, computed from the results of a mi nimum of 20 repeat tests made over 20 days on samples taken from a single homogeneous comme rcially available diesel fuel meeting applicable industry consensus an d federal regulatory specific ations with fuel marker solvent yellow 124 con t ent in the range of 0. 10 to 8 milligrams per liter. The 20 results must be a series of tests with a sequent ial record of analyses and no omissions. 3

A. In the workbook entitled “Fuel Marker Solvent Yello w 124 Template”, locate the worksheet entitled, “SY124 Precision”. Enter data in the light shaded green areas of the worksheet. Fo r an example of the “SY124 Precision” worksheet with data completely entered, please see t he worksheet entitled, “EX – SY214 Precisio n”. Notes : 1. Test results must be r eported in milligrams per liter(mg/l) to the number of signific ant digits specified in the method description or, if no such

1 In certain areas of the country, so lvent yellow 124 has to be used as a f uel marker in heating oil distillate fuel indefinitel y beginning June 1, 200 7 a nd, from Ju ne 1, 2010 thro ugh May 31, 2012, in lo co motive and marine distillate fuel.
2 § 8 0 .582 (b )(1).
3A laboratory may exclude a given sa mple or te st resu lt only if the exclu s ion i s for a valid re aso n und er good la borato ry pra c tice s a nd it maintain s re co rd s reg a rdin g the sa mple and te st result s and t he rea s o n for excludi ng them.

1precision is indicated, to as many digi ts to the right of the decimal point as appear on the instrument readout up to three. 2. The date and time of each test measurement must be reported. 3. Please include the laboratory test sample ide n tification number for each test result.

B. After enteri ng the data into the lightshaded green area of t he “SY 124 Precision” worksheet, go to the “File” menu at the top of the screen and se lect “Save” to save your data. Once all the data are entered into the “SY 124 Precision” worksheet, the standard deviation of the data set (located in cell B18), and an indic a tion a s to whether the SY124 precis ion criterion is met will be displayed b y the worksheet. The indication of “PASSED” or “FAILED” is located in cell B1 7 in the worksheet, after the question, “Is SY124 Precision Criterion Met?”. If the worksheet is missing required dat a, an indication of “REQUIRED DATA MISSING” will appear after this question. There is a QC data entry check for each test r e sult in column E (i.e., if dat a is entered in a test result cell, an indic a tion o f“OK” will appear ne xt to that ce ll, but if no data is entered in a test result cell, an indic a tio n of “DATA REQU IRE D IN CELL #” will app e a r next to that cell). Note : If the applicant wishes to include more than the 20 minimum tests, please report the additional data byadding r o ws to the spreadsheet. 4

II. Accurac y demonstration for solvent y e llow124 test method.

Accuracy Criteria - 1. The arithmetic average of a cont i n uous series of at least 10 tests performed on a commerciall y available marker sol v ent yello w 124 standard in the range of 0.10 to 1 milligrams per liter solvent yellow 12 4 shall not differ from the accepted reference value of that standard by more than 0.05 milligrams per liter. 5,6

2. The arithmetic average of a cont i n uous series of at least 10 tests performed on a marker sol v ent yellow 124 standard in the range of 4 to 10 mi lligrams per liter solvent yellow 1 2 4 shall not dif f er from the acc epted reference value of that standard by more than 0. 05 milligrams per l i ter. 7,8

4 Additio nal rows may be inse rted to accomm odate t he extra data points. If these ro ws are a dded in the middle of the data set (say arou nd row 2 5 ), the equat i ons that an al yze the data will be autom atically adju s ted. If d i fficulties are encounte r ed i n doing thi s , plea se call for help.
5 § 80.582(b ) (2)(i).
6As explained in § 80.582 (b)(2)(iii), indiv i dual test re sults sh all be compen sate d for any kn own chemi c al interferen ce s. 7§ 80.582(b ) (2)(ii).
8 As explained in § 80.582 (b)(2)(iii), indiv i dual test re sults sh all be compen sate d for any kn own chemi c al interferen ce s.

2A. Locate the worksheet entit led, “SY124 Accu racy”. Ente r data in the light shad ed green areas of the worksheet. For an example of the “SY124 Acc u racy” worksheet with data completely entered, please see the worksheet entitled, “EX - SY124 Acc u racy”. Notes : 1. Test results must be r eported in milligrams per liter(mg/l) to the number of digits specified in the method descr iption or, if no such precision is indic a ted, to as many digits to the right of the decimal point as appear on the instrument readout up to three. 2. It is recommended that the date and time of eac h test measurement be reported. 3. Please include the laboratory test sample ide n tification number for each test result. 4. In the appropriate rows, enter t he “Name of Standard Vendor”, “Standard Lot Identification Numb er”, and “Accepted Refe rence Value of the Standard (mg/L)” in milligrams per liter for both the 0.1-1 mg/L and 4-10 mg/L marker solvent yellow 124 s t andards. 5. Since the T e st Method and Laboratory Identi f ication information for this demonstration are the same as the Test Method and Laboratory Identification information in the “SY 124 precision” worksheet, for your convenienc e, this information is automat ically reference d from the “ SY124 Precision” worksheet.

B. After enteri ng the data into the li ght shaded green area of the worksheet as described above: 1. Go to the “File” menu atthe top of the screen and se lec t“Save” to save all of the entered data. 2. Once all data are entered into the “SY124 Ac curacy” worksheet, the worksheet will calculate the arithmetic average fo r both the 0.1-1 mg/L marker sol v ent yellow 124 data set (loc ated in cell B20) and the 4-10 mg/L marker sol v ent yellow 124 (located in cell I2 0). It will also calculat e the difference between the arithmetic average of the data set and the accepted reference value of each standar d (located in cell B24 for the 0.1

- 1 mg/L concentration and in cell I24 for the 4-10 mg/L concentration). 3. The worksheet will indicate w het her the marker solvent yellow 124 accuracy criteria are met for the candidate test method by saying

“ PASSED ” or “ FAILED ” in the cell after the que stions, “Is 0.1-1 mg/L marker sol v ent yellow 124 Accuracy Crit erion Met?” (located in cell B19) and “Is 4-10 mg/L marker solvent ye llow 124 Accuracy Criterion Met?” (located in cell I19). B o th of these accuracy criteria must be met in order for the test method to be consider ed to have demonstrated sufficient accuracy. 4. If the worksheet is missing requir ed data, an indication of “REQUIRED DATA MISSING” will appear after the app licable question. There is a QC data entry check for each test result in column E and column L (i.e., if data is entered in a test result cell, an indica tio n of “OK” will a p pear ne xt to that

3cell, but if no data is entered in a testresult cell, an indic a tion of “DATA REQUIRE D IN CELL #” will app e a r next to that cell). There is also a QC data entry check on the concentration of the standards in cell E23 and cell L23. Note : If the applicant wishes to in clude more than the 10 minimum tests, pleas e report the additional dat a by inserting rows into the spreadsheet. 9

Additio nal rows may be inse rted to accomm odate t he extra data points. If these ro ws are inse rted in the middle of the rang e (sa yafter row 30 ) the equat io n s for the average an d othe r function s wil l be automatically adju s ted. Extra ro ws insert ed for one of the two stan d a rd level s , wh ile appe arin g in the rang e for the other st anda rd level, will not affect t he calcul ation s for the level wh ere no d a ta were ad ded.

4 9PART II - Instructions for submission ofA ccuracy and Precision Information to Agency fo r Approval

I. For each test facilitythat w i shes to have a test method appro ved, the follo w i ng informatio n must besubmitted to the Agency :

A. For methods that are approved bya voluntary consensus-based organization standards body (VCSB) 10 , such as the American Society for Testing and Materials (ASTM) or International Standards Organization (ISO), each indiv i dual test facility must submit the informati on for accuracy and precision criteria specified under § 80.582(b) (Please use instru ctions in Part I of this document). The approv al of the test method i s limited to the single test facility that performed the testing for accuracy and precision. 11 The individual fa cility must submit the accuracy and precision results for each me thod, including information on the date and time of each test measurement to demonstrate precision, following procedures established by the Administrator.

B. For methods that are not approved by a VCSB 12 , for such a method to be approved, the following information must be submitted to the Administrator by each test facility for each test me thod that it wishes to have approved:

1. Full test met hod documentation, including a desc r iption of the technology and/or instrumentation that ma kes the method functional and all procedures that are part of the method. 13 2. Information demonstrating that th e test method meets the applicab le accuracy and precision criteria of § 80.582(b), including information on the date and time of each test measurement to demonstrate precision (Please use instructions in Part I of this guidance). 14 3. If requested by EPA, test results fr om use of the test method to analyze samples of commercially available distilla te fuel contain i n g the fuel marker solvent yellow 124 provided by EPA. 15 4. Any additional information reques ted by the Administrator and considered necessary for deciding whether to approve the test method.

C.

. Sample Re tention 16 Samples used for precision and accuracy determination must be retained for 90 days.

10 4 0 CF R 80. 582(c)(1 ).
11 Wher e a facility has mo re than onefunctionally identi cal instrume nt im p l ementing a si ngle me thod, only one of th e in stru me n t s mu st b equ alified(bu t statisti cal qu ality contro l mu st b eapp liedto eachinstru me n t , as ind i cated bel o w)

. 12 4 0 CF R 80. 585(c)(2 ).
13 4 0 CF R 80. 585(c)(2 )(i ).
14 4 0 CF R 80. 585(c)(2 )(ii )

. 15 4 0 CF R 80. 585(c)(2 )(iv )

. 16 4 0 CF R 80. 585(c)(2 )(iii ).

5D. Confide n tia l Business I n formation Cla im

. You may claim the information you submit as confidential business informa tion (CBI) by clearly marking your submission. Please be sure to indica te your CBI claim where asked on the spreadsheet and clearly indicate that your submission contains inf o rmation claimed as CBI in your cover letter. Ifno such written claim is made, then the information you submit may be made available to the public by EPA without further noti c e. EPA’s regulations r egarding CBI are at 40 CFR Pa rt 2.

Please send one paper hard copy of the information described above and a cover letter with your signature, along with a 3.5 inch floppy disk or compact disk containing the accuracy and precision data in the spreadsheet described abov e by overnight mail or courier se rvice to the address below.

Joe Sopata, Chemist United States Environmental Protection Agency Office of Air and Radiation Complianc e and Innovative Strategies Division Fuels Program Support Group 1310 L Street, N.W, (6406J), 6 th Floor, Room 627Q Washington, D.C. 20005

F. 17 EPA Ap proval

.

1. Within 90 days of receipt of all mate rials required to be submitted under 40 CFR 80.582(c)(1) or (2), the Administrator sha ll deter mine whether the test method is approved.

2. If the Administrator de nies approval of the test method, within 90 days of receipt of all materials required to be submitted under 40 CFR 80.582(c)(1) or (2), the Administra tor will notify the applic ant of the reasons for not approving the method. If the Administrator does not notify the applicant of disapproval or incomp lete information during that ti me span then the test met hod shall be deemed approved.

3. If the Administrator finds that and indi vidual t e st facility has provid ed false or inaccurate informati on under 40 CFR 80.582(c), upon notice from the Administrator the approval shall be void ab initio

.

4. The qualific ation of any test me thod under the require ments of 40 CFR 80.582 shall be valid for the duration ofthe period during which the fuel marker provisions remain applicable under the Motor V e hicle Dies e l Fuel regulations at 40 CFR 80 Subpart I.

4 0 CF R 80. 582(c)(3 ).

6 17G. Quality Assurance procedures for solvent yellow 124 measurement instrumentation

. 18 A test will not be consider ed to have been made with an approved test method unless the followi ng quality control procedur es are performed separately for each instrument used to make measurements:

1. Follow all m andatory provisions of ASTM D 6299-02 and construct control charts from the mandatory quality cont rol testing prescribed in paragraph 7.1 of the reference method, following guidel ines under A 1.5.1 for indiv i dual observation charts and A 1.5.2 for moving range charts. 19

2. Follow par agraph 7.3.1 of ASTM D 6299-02 to test check standards using a reference material at least monthl y or following any major change to the laboratory equipment or te st procedure. Any deviation from the accepted reference value of a check standard gr eater than 0.10 milli grams per liter must be investigated.

3. Samples of test batches must be retained for 30 days or the period equal to the interval between quality contro l sample tests, whichever is longer.

4. Upon disc overy of any quality cont rol testing violat ion of paragraph A 1.5.1.3 or A 1.5. 2.1 of ASTM D 6299-02, or anycheck standard deviation greater than 0.10 milligrams per l i te r, conduct an investigation into the cause of such violation or dev iation and, after restoring method performance to statistical control, re test retained samples from batches originally tested since the last satisfactory qu ality control material or check standard testing occasion.

H. 40 CFR 80. 582(d)(5). Record retent ion requirements for approved test methods

. Each ind i vidual test facility must retain records related to the establishment of accuracy and precision values, all test method documentation, and any qualit y control test and analys is under title 40 CFR sections 80.582 for five years.

18 4 0 CF R 80. 582(d).
19 T he Di re cto rof the Fede ral Regi ster a pprove d the inco rpo r atio n by refere nce of ASTM D 6299-02, Standard Pra c tice fo r Appl ying Statistical Qualit y Assuran c e T e chn i que s to Evaluate Analytical MeasurementSystem Performa nce, as pre s crib ed in 5 U.S.C. 552(a) and 1 CF R Part 51. Anyone may purcha s e cop i es of this sta ndard from th e American S o ciety for Te sting and Mate rials, 10 0 Barr Ha rbo r Dr., We st Co nsh oho cken, PA 19428. Anyone may in spe c t co pie s at the U.S. EPA, Air and Radiation Docket and Information Center, 1301 Constitution Ave., N.W ., Room B102, EPA West Building, Wa shin gton, D.C. 204 60 o rat the Natio nal Archives and Record s Administratio n (NA R A). For inform ation on the availa bility of this material at NA RA, call 202 -741-603 0 or go to: http://www.a r chive s .gov/federal _r egiste r /code _of_fed eral_ r e gulatio ns/ibr _lo c atio ns.html

.

7EPA Co ntact:

Joe Sopata (202) 343-9034 Fax: (202) 343-2801 Email : sopata.joe@epa.gov

OMB Control No. 2060-0308 Approval expires: December 31, 2011

The public reporting and recordkeeping burden fo r this collection of informati on is estimated to average 180 hours per response. Send comments on the Agency’s need for this information, the accuracy of the provi d ing burden estimates, and any suggested methods for minimizing responde nt burden, including through the use of automated collection techniques to the Director, Collection Strategies Divis ion, U.S. Environmental Protection Agency( 2822T), 1200 Penns ylvania Ave., NW, Washington, D.C. 20460. Include the OMB c ontrol number in any correspondence. Do not send the completed form to this address.

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