ML20059E166

Submits Addl Comments on Toxics Monitoring Program.Util Sent Request to K Roller to Allow Licensee to Use Alternate Detection Limits for Chemical Analyses in Subj Program.Ltr Containing Request Encl

ML20059E166
Person / Time
Site:	North Anna
Issue date:	08/29/1990
From:	Marshall B VIRGINIA POWER (VIRGINIA ELECTRIC & POWER CO.)
To:	Kregloe W VIRGINIA, COMMONWEALTH OF
References
NUDOCS 9009100062
Download: ML20059E166 (13)

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1 Mr. William L. Kregloe l Virginia Water control Board i Valley Regional Office  !

116 North Main Street P. O. Box 268 Bridgewater, VA- 22812 ret ADDITIONAL COMMENTS ON DRAFT VPDES PERMIT FOR NORTE ANNA POWER STATION

Dear Mr. Kreglost ,

l In! earlier comments we requested that sections of the Toxics ,

Monitoring Program (TMP) specifying minimum detection limits for I chemical analysis be removed. The request was based on the Board's inadequate justification for the limits given. Though the Board's i response to our comments did identify the source of the limits,  !

adequate justification is still absent and our need for relief from i these unrealistic monitoring requirements still exists. l 1

V i rg ini a Power has sent a request to Mr. Ken Roller,to allow us to 1 use alternate detection limits for chemical analyses in the TMP. )

A copy of the letter containing that request is attached and our )

justification for alternative limits is included in the letter. i We wish to have this letter and - the accompanying letter to Ken Roller made part of the official record as well as serve as a request for alternate detection limits as allowed under section C.2.B.-of the draft permit.

Sincerely, f: , !

B. M. Marshall, P.E.

Manager

- Water Quality t.

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9009100062 900829 PDR ADOCK 05000338 P PDC w

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. i Mr. William L. Kregloe August 29, 1990 Page 2 '

I cc U.S. NRC Docket No. 50-338/50-339  ;

101 Marietta St., NW Suite 2900 i Atlanta, GA 30323 U.S. NRC Attnt Docket Control Desk i Docket No. 50-338/50-339

• Washington, DC 20555 l NRC Senior Resident Inspector Docket No. 50-339/50-339 ,

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August 29, 1990 Mr. Man W. Rollar Virginia Water cartrol Board 2111 Hamilton Struct P. O. Boit 11143 Rictsacrid, VA 23230 RBs NEOWF 70m grsunamirs terscTZtal LDtITE - VIREDER m Dear Mr. Roller Under the 'n:ncicas Manaoament F.,.m, all of our pcwor stations must begin to tast and report priority pollutants this year as their vites permits are reissued. 'Ihis letter is provided to you in support of our request for alternate detection limits allowed under this program and is in specific rampanse to your request of February 6,1990 for additional information on this subject.

As you knew, the detection limits required in our permits are based on thans given in Methods for chemical Analyses of Water and Wastawetar (*:hW), W h 1983. 'Ihm fundamental point of ocntention we raise is whether or not the tas .5 in the 1x:hW are accurate. It is indeed stated in the marsaal that such limits are considered to be the " minimum working limits adtievable with the prMwas given. . . " 'Ihis position, however, we and others do disp %. 'Ihe dp has been the subject of a lawsuit the 4th cira. tit oc= t A @eals and of numerous studies and publicati by the Electric PL lammatt:h Instituta (EPRI) and others. Perhaps a note thorough discussion wit _. ster understanding of the potential for problems that we see arising frun specifying such detection limits.

At issue is whether methods approved in 40 CTR Part 136 have been adequately validated; whether the performance characteristics, i.e. the precision, bias and limits of detection, have been established by hw %iate methodology and are available to the regulated ocununity. Detection lim:,ts found in the literature or derivable frau data frun the literat'.tre as ocatpared with those contained in 3

the MCAW are generally higher, sometimes by an order of magnitude . 'Ihe EPA 1 Virginia Electric & Paar co., r1 al. v. U. 8. Erwirtriental Protection A0ery, Docket le. 84 2221 2 /uppaa Diemergus frun Steerttectric Paar Plt,1ts: The Precisie)artillas of Metteds for Denical Aretwis, EPRI CF3744, Electric Paar Researth trutitute, Pelo Alto, cA 935, ikw.1996 3lbid 1 I

4 actually performed asweral staxiias"" Wie prd* precisica and bias data frtan 2: ch limits of detection for acsua metal parumstare can be calculated. Em declined to do so claiming that analyta ocncentrations measured were too high to produos data that oculd be used to calculate a method detetion limitt hcWever, in many instances the method studies were conducted at canoantrations that most DA's own critaria as stated in 40 CFR Part 136, Apperxiix B. Using EPA data frtet Mothed Study'31 for furnmos atcanic absorption, nothod detmotion limits have been calculated frtan data generated by both a single cperatar and by a grtap of laboratories. 'Ihe calculation is based on regression equations that dancribe EPA's data. 'Ihe method detecticn limit is defined as the level abcwe pch the anal has 99% confidence that the analyte being measured is present. It is tively apparent that the precisica of measurenant achasved by a single laboratory will be battar than that achieved among a grtap of laboratories. However, the only way to verify the accuracy of any result is by ocuparisen with that of another laboratory. '1 hat is why detecticn limits determined by interlaboratory studies are the most appropriata.

'Ihm following table ocupares the detecticn limits for the graphite furnace method for several metals for m.titiple laboratories ocupared to the detection limits stated in our permits. Analyte was measured in reagent grade water except as noted.

'mata 1 IWiscTItaf LIMr!5 FIO( DA WRM G3GNIE 'IO PEltGT LIMHW

i. MIIATPIE PEltGT PAIUMETER EA E Rh't G E M LIMIT Armenic 14.3 10 Copper 11.2 1 Imad 6.9 1 Nickel 22.2 10 Selenium 14.6 10 Silver 1.7 (SW) 0.2 (SW) = Surface Water 4 U.S. EPA teethod st@ 31 trace wtate tv Ateie Abneratim marece techniamsl. Finst Report EPA Cmtract Ido. 68-(B 3002, U.S.

EPA Erwirapuntal Mmitorire arn SL4;xrt Laccretary, Ctrcirvati, 0145268, Feb.1915.

5 EPA Hethod st@ 27. Ierthod 200.7 tente stetets tw ICP. Firal Resurt EPA Ccntract ho. 68-(B 3007, U.S. EPA Erwirusuntal hmitwire ard 3lgurt Laturstory, Circimett, Qt 452e8, Feb.15.

6 LMPA teethod St@ 7. Anatumes for frece flanants in unter, tw Atomic Abnerettan bu-- = (Direct Anoiraticro and coterlantry.

U.S. EPA Erwitwsuntal Monttertry are honearth laboratory, Cirettrutt, 01 45268, Msy, 1 2 .

7 80L e S x t thert 5 e precisim (starstrd deviatim) are t a sirgle tailed "t" statistic for the 99% confiderte leel with aggrtgriate caugrees of freetta l

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'Ihm fundamental point of measurement is to be able to detect the presence of a paruester, that is, to distinguish a ocmoentration graatar than sero with a certain defined degree of confidanos. As you will note, EPA's own data on the method indientes that detamining the prueenos of parameters such as armonic, oper, lead, nickal, selenius, arxi silver with 99% confidence may be difficult if we are held to the rid

• ion limits listed in our pemits. We therefore request alternata detecticn limits for the parenstars based on this DA study as shown in Attactuant 1. Even limits derived frca DA data are q+4=4=*i" because EPA eliminated frtei oansideration a large amount of data that is designated as " outlier" data. 'Ihis was done with insufficient justificaticef. i

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It should be r-gJ. zed that method detection limits detamined for analytes ,

dimanived in ruegent grade water are those achievable unders ideal conditions.

Any other matrix, sus as would be represented by a station's discharges any introduon intarferunoes that would likely result in higher detectimt limits.

If we find this to be the case, alternata detection limits wculd be requested.

If quantification as opposed to mare detection of these paramstars is required, than data collected at the pemit detection limits is entirely inadequate. EPA l Imoognizes that analytical results at or near the method detecticm limit do not ,

have sufficient accuracy for quantification. EPA inttnMnari the m vi. of a '

" practical quantification level", the lowest level that can be reliably achieved within specified limits of precision and accuracy during routine laboratory  ;

operating canditions. In order to be able to reliably measure the canoentration ,

of a particular parameter with a precision of at least 120%, it is usually

• considered that the measurement must be anywhere frtu 5 to 10 times higher than the method detection limit'. If the Boarti intends to oansider data sutanitted for

• any of the parameters listed in the ' IMP to i.p. -- i. the actual canoentrat$cn -

present, than we propane to i.mi. canoentrations detected at 7.5x the method r detection limit. Below such canoentrations, we should only be required to +t.

[ " detected" or "not detectad",

t For detection of organic parameters, the pemit states that the limits of .

detection given in 40 CIR Part 136 for Methods 624 and 625 nust be met. Such numbers suffer frcan the same limitations as those listad in the MCAW for the <

metals methods. 'Ihey are not reliable detection limits haned on a Valid [

evaluation of the methods. Again, nore approprigts detection limits are 4 derivable frun method studies performed by EPA . In the absence of these detection limits, which would likely be higher, our laboratory is in the process of establishing, as a single operator, method detection limits using reagent '

, grade water. Scna determinations are cartplete anci a list of the alternata '

! detection limits achieved by our laboratory are listad in Attachment A.

8 coments admitted ty tre utility Water Act Grue cn the Frwonet to murd 40 cm Part u6 r, palettes p@lished ty the a

drawernal Protectivi Aorry, $ssaamer 3,1967. 52 m II, 542 $7

% M the prestle to prgomed hatterni Prieury Drir*ity senter RepJtettas for Volatile Sy1thetic 01pnic omsicals (Fed.

q o, Nueer 13,1915) " ...Fes wv ee@ted haned tsun the Kt ed an estinate of a hi pier i Lewt Witch tauld rgsrsarit

. J ttutinrty amientde teset with relttively pxc certairfy that the reported velut is reliable. Tradittently,

. taan estinetso et 5 to 10 ttres the Kr. Era telleves that settire the Ni.s in a rese tetimen 5 to 10 tless the y the tant laboratories is a fair eenetatisi for post State ard cometrial laterstories." +

, 20 Method 624 a f\riddes k h #wthari 625 - Bene luutrats 11 The p. "ticr) (8 alt of 1 ta/t carrot te achlewd ty tte cold vapor nethod ad a new FIAS trstrumrt has teen orderud. The nethod .. tim 9 will te artermirad at a later tine.

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e Additional deemuMaticms of alternata limits will be performed but the proomas is very laborious. Even EPA has ret dotarained a limit of detecticm for all of the paramsters analyzed by Methods 624 and 625. mare such limits are absent, it han been rated in the attamment.

It should be apparent that requirirg, en names, the 9*ir*n limits of Methods 624 and 625 will lead to ocupliance problems regardless of idhether ce ret tcacic organic compounds are present in our discharges. We suggest that alternata limits of detecticm are absolutely essential and feel that a recognitice of both those we have tkaas far baan able to dotaraine and those yet to be dotarained as

. legitimata alternatives is nanded. Prun these, the %Wata limits that must be reported can be established. As we refine the information cm caganic analysis, it will be prwided to you.

The Virginia Power Systen Laboratory has thus far nede every attanpt to prwide data at levels requestad by the Virginia Water pl Board. 7his has ===H===

meant purdiasing new equipment, as for mercury , or p=a ing ramarous method validating analyses. We are also requesting an alternata method for cyanide analysis. A method detection level for the Selective Electrode Method (frun Standard Methods #412 E) has baan determined by our laboratory to be 27 ug/1.

This method yields, in our laboratory, more reliable data at a raamanable detection level than any of the methods listed in Part 136.

As for the nonsurunent of total phenols, it is difficult to understand why the analysis nand be done at all. If there is im Water Quality critaria or proposed standard for total phenols, perhaps this analysis is not appropriata under the TMP to begin with. Method 625 yields informaticm on eight individual phenolic ev= =inds. The water quality starstard is for phenol and it would assa sus analysis would be sufficient.

These cxamaants are made to help clarity our earlier requests. If additional d4=m== ion would be helpful we would be glad to meet with staff nembers at their convenianos. Maantina, we wish to have thane ocenants serve as a recpast for alternata detection limits.

Sincerely,  !

A B. M. Marshall, P.E.

Manager Water Quality l

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. Note-l--Mercury MDL'will be determined with new FIAS instrument. '

Note 2 - Cyanide is determined by Specific Ion Electrode and manufccturer lists lower reporting limit O 130 ug/1.

Note 3 - MDL values were determined in laboratory standards prepared in' deionized water. .

Note 4 - Multilevels of' laboratory standards were repeated for MDL determination.

Note 5 - Options used for EPA Method 625

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