&EPA
            United States
            Environmental Protection
            Agency
             Office of
             Water Programs
             Washington DC 20460
Norfolk Va.
January 17-18, 1980
             Water
Seminar for Analytical
Methods for Priority
Pollutants
            Norfolk, Va.
            January 17-18,  1980


             Effluent Guidelines Division

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xvEPA
           United States
           Environmental Protection
           Agency
           Office of
           Water Programs
           Washington DC 20460
Norfolk Va.
January 17-18, 1980
           Water
Seminar for Analytical
Methods for Priority
Pollutants
           Norfolk, Va.
           January 17-18, 1980
           £
USB)
           Effluent Guidelines Division

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                             PREFACE

          The Effluent Guidelines Division of EPA has been
sponsoring a series of meetings to promote the free exchange
of technical information among contractors,  EPA personnel,
and various industry groups concerned with analytical methods
for the measurement of priority pollutants.

          This paper summarizes the proceedings of a meeting
held in Norfolk, Virginia,  on the 17th and 18th days of
January, 1980.

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                        Table of Contents
January 17, 1980

Title

Introduction
Microextraction Method
for Sample Preparation
Evaluation of Stable
Labled Compounds as
Internal Standards for
Quantitative GC/MS
Analysis

Priority Pollutant
Methodology Quality
Assurance Review,
Region VII

Examination of Mass
Spectral Data Tapes
for Characterization of
Sample Composition

Precision and Accuracy
Studies

Precision and Accuracy
Studies

Verification Procedures
Results to Date
Speaker                       Page

William Telliard                1
EPA/EGD
Robert Schaffer
EPA/EGD

John Rhoades                    7
Southwest Research Institute
Kathleen Thryn
Arthur D. Little, Inc.
William F. Cowen
Catalytic, Inc.

Dr. Price E. Colby             52
Systems,  Science and
Software
Robert D. Kloebfer             97
EPA/Region VII
Walter Shackelford            117
Environmental Research
Laboratory
Michael Carter                135
EPA/EGD

Robert G. Biemer              145
TRW

Dean Neptune                  160
EPA

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                        Table of Contents

January 18, 1980

Title                        Speaker                     page

Introduction                 William Telliard             195
                             EPA/EGD

Evaluation of Candidate      Jim Longbottom               211
Compounds in Surrogate       EMSL-Cincinnati
Spikes

Proton Induced X-Ray         Michael Carter               231
Emission Elemental           EPA/EGD
                             George Grant
                             Virginia Associated
                             Research Campus

Preliminary Methods for      Joan Fish                    291
Organic and Elemental        Vyer
Analysis of Sludges

Conclusion                   William Telliard             321
                             EPA/EGD

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  I
  I

 1                            INTRODUCTION
 2                     BY:  WILLIAM TELLIARD
 3                          POBERT ^CHAFFER
 4 i
 5                                MR, TELWn:  GOOD MORNING,
  i
 e |      MY NAME is BILL TELLIARD, AND I'M FROM FpA,  fls SOME
  I
 7 |      OF YOU MAY OR MAY NOT KNOW, WE'VE DONE THIS BEFORE, SO
 8 !      THIS MORNING, TO GET THINGS STARTED OFF, WE'D LIKE
 9 j      TO HAVE BOB SCHAFFER, THE DIVISION DIRECTOR FOR Ef;D,
10 I      SAY A FEW THINGS, AND THEN WE HAVE A WHOLE LIST OF
11 !      ANNOUNCEMENTS AND PROMISES TO MAKE YOU, AND THEN WE'LL
12 |      GET TO THE FIRST SPEAKER,
13 i                               MR. SWFFFP:  nNCE AGAIN,
14 i      WELCOME TO NORFOLK AND OUR SEMINAR ON ANALYTICAL
15 |      METHODS FOR PRIORITY POLLUTANTS,  I WAS THINKING ON THE
16 |      WAY DOWN, THE ONE REASON I GET TO COME  IS BECAUSE  I'M
17       PAYING FOR IT,  WE DON'T HAVE TO HAVE ANY KEYNOTE
18       SPEAKERS OR ANY DIGNITARIES HERE TO GET A PRETTY GOOD
19       CROWD, SO IT LOOKS AS IF YOU'RE ALL INTERESTED  IN  THE
20 |      SUBJECT MATTER,  I HOPE YOU'LL HAVE A GOOD SESSION,
21             I DON'T HAVE A GREAT DEAL TO SAY,  WE'VE BEEN
22       HERE BEFORE, AND SOME OF YOU WERE HERE  YESTERDAY AT
23       CHEMICAL MANUFACTURERS ASSOCIATION MEETING WHO HAD A
24       SIMILAR SESSION, AND YOU MAY GET SOME OF THE  INPUT
25       FROM THEIR DELIBERATIONS AS WELL TODAY,

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 1        SINCE  OUR  LAST MEETING, WE'VE MOVED  INTO THE  PHASE  OF
 2        PROPOSING  REGULATIONS BASED ON THE DATA THAT  WE'RE
 3        GATHERING  USING THE METHODS THAT YOU'VE BEEN  DEVELOPING,
 4        I  SAY  THE  METHODS THAT YOU'VE BEEN DEVELOPING BECAUSE
 5        THEY ARE STILL EVOLVING, AND WE'RE AWARE OF THAT,   WE'VE
 6        COME A LONG WAY IN THAT WE KNOW A LOT MORE ABOUT WHAT
 7        WE'RE  DOING AND WHAT OUR DATA MEANS  AND WHAT  TOXIC
 8        POLLUTANTS NEED TO BE CONTROLLED IN  WHAT INDUSTRIES,
 9        K'E'VE  TRIED SOME NEW APPROACHES IN THE PROPOSED REGU-
 10        LATIONS, AND WE'LL TRY MORE IN THE FUTURE, AT LEAST
 11        UNTIL  WE'RE ABLE TO USE THE SPECIFIC METHOD TO SET  A
 12        LIMIT  FOR  A SPECIFIC TOXIC MATERIAL.
 13            WE'RE NOT TOO CONCERNED ABOUT THE FACT THAT WE
 14        DON'T  BECAUSE WE STILL FEEL WE'RE ABLE TO CONTROL THE
 15        TOXIC  POLLUTANTS WITH THE APPROACHES THAT WE  HAVE
 16        AVAILABLE  TO US,
 17            ANALYTICAL CHEMISTRY is A FIELD THAT  is  NOT
 18        FAMILIAR TO MANY FOLKS OUTSIDE THIS  ROOM,   I  THINK  THAT
 19        WHAT WE'RE DOING,  IN A SENSE,  is DRAGGING THE AGENCY,
 20        ALBEIT KICKING AND SCREAMING,  INTO THE FOREFRONT OF
 21        ANALYSIS OF ENVIRONMENTAL SAMPLES FOR SPECIFIC ORGANIC
 22        COMPOUNDS,  I KNOW THAT MANY OF YOU  HAVE SPENT HOURS,
 23        SOME VERY  FRUSTRATING, IN MAKING WHAT PROGRESS WE HAVE
24        TO DATE,   I THINK THAT THE EFFORT WILL CONTINUE FOR A
25        PERIOD OF  TIME AND PROBABLY EXPAND,  WE WERE  TALKING

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1        A LITTLE BIT YESTERDAY ABOUT MATRIX EFFECTS AND SO
2        FORTH;  WE'LL PROBABLY HAVE A FEW MORE WHEN WE GET
3       INTO SOLID WASTE SAMPLES,   WE'RE LOOKING TO MOVE INTO
4       THIS AREA WITH THESE ANALYTICAL TECHNIQUES OR SIMILAR
5       ANALYTICAL TECHNIQUES,  As MANY OF YOU KNOW, SOLID
6       WASTE IS THE NEXT AREA THAT THE AGENCY IS MOVING INTO,
7       THE REGULATION AND CONTROL OF THE DISPOSAL OF
8       HAZARDOUS MATERIALS,
9            I  WANT TO COMPLIMENT YOU ON YOUR PATIENCE AND
10       DILIGENCE,  WE'RE TRYING VERY HARD TO MAKE SURE THAT
11       THE FEARS OF THE ONES THAT ARE BEING REGULATED BY
12       OUR EFFORTS ARE ALLEVIATED TO A DEGREE.  WE'RE TRYING
13       TO MAINTAIN THE POSITION THAT WE REALLY AREN'T GOING
14       TO DO SOMETHING CRAZY WITH THE DATA WE'RE GATHERING;
15       NOBODY BELIEVES US YET, BUT WE'RE GOING TO PERSIST,
16       WE DO NEED THE HELP, WE DO NEED SUGGESTIONS,  BEING
17       ON THE FOREFRONT, WE ARE DEVELOPING REGULATIONS AND
18       METHODS AT THE SAME TIME,  IT  IS A LITTLE BIT UNIQUE;
19       RATHER THAN HAVING TOOLS AVAILABLE TO  US, WE HAVE TO
20       DEVELOP THE TOOLS AS WE'RE GOING ALONG,
21            I HOPE YOU HAVE ANOTHER SUCCESSFUL MEETING AND
                                                                 !
22       THAT YOU  GET  SOMETHING OUT OF  IT, AND  IF WE  HAVEN'T      |
                                                                 I
23       SOLVED ALL THE PROBLEMS BY THE  END OF  TOMORROW, WE       |
                                                                 t
24       MAY HAVE  ANOTHER ONE  NEXT YEAR,  WE'RE SUSPICIOUS THAT
25       WE'VE GOT ALL THE PROBLEMS SOLVED; THAT'S  WHAT  BlLL

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 1        TOLD ME EARLIER,  ANYWAY,   NOW I'LL TURN THE PROGRAM



 2       BACK OVER TO RlLL,   I  WILL BE AROUND FOR THE REST OF



 3       THE DAY,   IF THERE  ARE ANY PARTICULAR QUESTIONS THAT



 4       YOU HAVE  ABOUT SOME OTHER ASPECTS OF THE PROGRAM,  I'D



 5       BE HAPPY  TO CHAT  WITH  YOU,
   i


 6 !                               MR,  TELLI.^RD:   THANK YOU,



 7 j      WE HAVE A COUPLE  OF QUICK ANNOUNCEMENTS,   ONE IS,  IF



 8 !      EVERYONE  MAKES SURE THEY  PLEASE REGISTER,   K(E WANT TO



 9       MAKE SURE YOU REGISTER BECAUSE THAT'S WHERE WE GET THE
   !


 10 !      LIST TO SEND OUT  THE INVITATIONS IF THERE  IS ANOTHER



 11        ONE OF THESE SOME DAY,  V/E HAVE A COUPLE OF BREAKS



 12       SCHEDULED,   l*!E ALSO HAVE  AN OPEN SESSION TODAY, WHICH



 13       IS THE END PRODUCT  OF  PEOPLE SAYING WHAT ABOUT AND



 14       WHAT ABOUT AND WHAT ABOUT,   $0 THERE ARE A COUPLE OF



 15       FOLKS WHO ASKED TO  HAVE NOT REALLY A BIG CHUNK OF



 16       TIME,  SO  WE JUST  OPENED THE SESSION AND SAID FINE,



 17        IT STARTS AT 4, AND IT WILL RUM UNTIL THE  BAND STARTS



 18        PLAYING,  AND WE CAN DO THAT,  AND IT'S KIND OF AS LONG



 19        AS YOU FOLKS WANT TO HAMMER ON SOME STUFF —EVERYTHING



 20        EXCEPT TUNING YOUR  INSTRUMENT,



 21             THE  FIRST SPEAKERS TODAY ARE GOING TO TALK ABOUT A



 22        MICROEXTRACTION PROCEDURE THAT IS BEING UTILIZED BY



 23        THE  ORGANIC  CHEMICALS  BRANCH FOR ANALYSIS  OF,  RIGHT     I



 24        NOW,  A  GREAT DEAL OF IN-PROCESS SAMPLES,   THIS  PARTICULAR

                                                                 I


25        METHODOLOGY  IS UNIQUE  TO  THE ORGANIC CHEMICALS  BRANCH    j

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BECAUSE THEY'RE THE ONLY ONES DOING  IT,   So  WE  THOUGHT
WE WOULD LIKE TO HAVE THEM SAY  SOMETHING  ABOUT  IT SO
MAYBE SOME OF US CAN FALL BY THE WAYSIDE  AND TRY  IT,
TOO,
     WE'VE GOT THREE SPEAKERS,  AND WE'D LIKE TO HAVE
YOU HOLD YOUR QUESTIONS UNTIL EVERYBODY IS DONE.   THE
FIRST ONE is JOHN RHOADES FROM  SOUTHWEST  RESEARCH
INSTITUTE,  THE SECOND PERSON WILL BE  KATHY  THRUN
FROM ADL, A, D, LITTLE; THEN BILL COWEN FROM
CATALYTIC,  JOHN, DO YOU WANT TO START?

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i           MICROEXTRACTION METHOD FOR SAMPLE PREPARATION
2                        BY:   JOHN RHOADES
_                             KATHY THRUN
o
                              WILLIAM COWEN
4
5                                MR,  RHOADES:  I  KNOW THAT
6       YOU'RE ALL WELL AWARE OF THE FACT THAT THE GAS
7       CHROMATOGRAPHY WITH ITS SELECTIVE DETECTORS IS
8       THE PRIMARY INSTRUMENTATION AND TECHNIQUE USED
9       FOR THE DETERMINATIVE STEPS FOR MOST OF THE
10       PRIORITY POLLUTANTS,   UNFORTUNATELY, THERE IS
11       A SAMPLE PREPARATION REQUIRED BEFORE ANY OF THIS
12       GC ANALYSIS,  NOW, THE PRESENT APPROACH,  AND I'M
13       SURE THAT YOU'RE WELL AWARE OF THIS AGAIN, IS TO
14       TAKE A LITER OR A HALF A LITER OF WASTEWATER AND
15       EXTRACT IT MULTIPLE TIMES WITH SEVERAL MILLILITERS
16       OF SOLVENT,  Now, THERE'S SEVERAL DIFFERENT
17       DETAILS ON THIS ONE, BUT I'M GOING TO LUMP THESE,
18       AT THE MOMENT, INTO WHAT I'LL CALL THE EXHAUSTIVE
19       EXTRACTION APPROACH TO DIFFERENTIATE WHAT  I
20       PROPOSE TO TALK ABOUT  IN A MINUTE,   NOW, WITH THAT
21       APPROACH, THEN, THE COMBINED EXTRACT  IS USUALLY
22       CONCENTRATED  IN A  K-D  AMD USUALLY  FOLLOWED BY
23       SOME  FORM OF COLUMN CHROMATOGRAPHY CLEANUP,
24       I'M SURE YOU'RE ALL PRETTY WELL  AWARE OF THIS,
25

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25
  NOW.,  IN THEORY, THIS  IS A GOOD APPROACH,   THERE'S
ABSOLUTELY NOTHING WRONG WITH  IT,  YOU DO RUN  INTO SOME
PROBLEMS IN ACTUAL PRACTICE,   IF YOU'VE BEEN
OUT  IN  THE LAB AND DONE SOME OF THESE, NAMELY,  YOU
HAVE PROBLEMS TO SOME EXTENT WITH EMULSIONS; THERE IS
ALSO A  LOT OF GLASSWARE TO KEEP CLEAN, YOU  HAVE TO BE
QUITE METICULOUS;AND WHAT I BELIEVE  is BECOMING ONE  OF
THE  PARTICULAR PROBLEMS WITH IT IS THAT YOU MAY BE
EXCESSIVELY EXTRACTING  INTERFERING MATERIALS,   So  IT
REALLY  WORKS BEST WITH  FAIRLY CLEAN  SAMPLES,
  NOW,  WE HAVE BEEN USING AN ALTERNATE EXTRACTION  APPROACH
AT SOUTHWEST RESEARCH INSTITUTE, IT  HAS CONSIDERABLE
PROMISE  AND  HAS BEEN  LABELED MICROEXTRACTION  FOR THE
LACK OF ANY BETTER NAME; BUT  BASICALLY, MICROEXTRACTION
IS VERY SIMPLE.  IT'S A SINGLE EXTRACTION OF AN AQUEOUS
SAMPLE  WITH A VERY SMALL VOLUME OF SOLVENT, NOW,  THERE'S
NO FIXED RATIO OF SAMPLE TO SOLVENT,  IT CAN BE  AS  HIGH
AS 1,000 TO 1; GENERALLY WE PREFER TO WORK  IN  THE  RANGE
OF 100 TO 1  TO 10 TO 1, AND WE'RE ATTEMPTING  TO STANDARDI
ON SOME VOLUME IN THIS RANGb, NOW, BEFORE  I GO INTO THE
DETAILS AND THE MECHANICS OF THE ACTUAL EXTRACTION,  I'D
LIKE TO MAKE A COUPLE OF OTHER COMMENTS AND SHOW YOU SOME
CURVES WHICH HOPEFULLY  WILL GIVE YOU A LITTLE BIT  BETTER
 FEEL FOR THE POSSIBILITIES OF THIS APPROACH,
  NOW,  FIRST OF ALL, I  WOULD LIKE TO SAY THIS,THAT THE
ZE

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1       MICROEXTRACTION APPROACH DEPENDS ON BASICALLY TWO THINGS;;

2       THAT YOU DO, IN FACT, GET QUITE GOOD RECOVERY IN THE

3       SOLVENT PHASE, AND  TWO, THAT THE PARTITION COEFFICIENT
                    "
  i

4       IS REASONABLY CONSTANT OVER THE RANGE OF INTEREST,
  i
5 |     WELL, AS YOU CAN SEE,,THERE'S NO HIGH-POWERED MATHEMATICS


6      INVOLVED HERE.  WHAT I WOULD MERELY LIKE TO SHOW HERE
  l

7      IS THAT IF WE LOOK AT EQUATION I,  ALL IT REALLY SAYS

8 '     HERE IS THAT IF YOU ADD UP THE AMOUNT WHICH IS IN THE

9 |     SOLVENT AND THE AMOUNT WHICH IS IN THE WATER YOU, IN

10 !     FACT, HAVE THE TOTAL AMOUNT THAT'S IN THE SAMPLE; THAT'S


11      PRETTY STRAIGHTFORWARD,


12        THE NEXT EQUATION (II), WHICH IS THE ONE THAT WE HAVE SOME
  i
13 |     USE FOR,  MERELY SAYS IF YOU DIVIDE THAT AMOUNT WHICH

14 j     IS IN THE SOLVENT BY THE TOTAL AMOUNT, MULTIPLY IT BY

15      100, YOU HAVE THE PERCENT WHICH IS IN THE SOLVENT,
  I
16 |     So IN OTHER WORDS, WE CAN CALCULATE THE PERCENT WHICH
  i

17      SHOULD BE IN THE SOLVENT IF WE KNOW THE VOLUME OF THE

18      SOLVENT, THE VOLUME OF THE SAMPLE, AND THE PARTITION-

19 I     ING COEFFICIENT,  NOW, USING THIS EQUATION, I'VE DRAWN


20 i     UP A NUMBER OF CURVES HERE WHICH GIVE US SOME  IDEA OF
  i
21 |     HOW EFFECTIVE, AT LEAST IN THEORY, THIS APPROACH TO
  i

22      EXTRACTION MIGHT BE FOR A NUMBER OF DIFFERENT  PARTITION-

23      ING COEFFICIENTS,  NOW, YOU CAN GO EITHER WAY  ON THIS. As
  !
24 |    I USE IT, THE PARTITIONING  COEFFICIENT  IS THE RATIO


25      OF THE CONCENTRATION IN THE WATER TO THE CONCENTRATION

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I,       AX + BZX = TOTAL AMOUNT

                       1QDA
II,      % IN SOLVENT  =~T
     WHERE:   A-VOL SOLVENT (ML)
             B = VOL, WATER (ML)
             Z = PART COEFF,
             X = CONC,  IN SOLVENT
             ZX - CONC,  IN WATER
                       9A

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                                 % Recovery vs. Partition Coefficient (PC)
0    1
23456
   ml Solvent/100 ml H90

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 1        IN  THE  SOLVENT;  IF  YOU  WANT TO FLIP IT AROUND THE



 2        OTHER WAY,  WHY,  YOU GET THE RECIPROCAL NUMBER,



 3        WE  CAN  SEE  HERE  THAT IF WE  HAVE A MATERIAL THAT



 4        EXTRACTS  QUITE WELL INTO THE SOLVENT,  AS MOST OF THE



 5        PRIORITY  POLLUTANTS APPEAR  TO DO,  WE CAN GET A



 6        RECOVERY  ON MOST OF THEM OF 80 TO 100 PERCENT,   IT MAY



 7        DO  THIS NATURALLY,  OR  IT MAY BE FORCED BY SATURATING



 8        THE AQUEOUS SOLUTION WITH SALT,   AT ANY RATE, ON A



 9        THEORETICAL BASIS YOU CAN SEE HERE IF YOU HAVE A PAR-



 10        TITIONING COEFFICIENT OF SOMEWHERE IN THE RATIO OF 1,000



 11        TO  1, USING 100  MILLILITERS OF WATER,  YOU CAN EXTRACT



 12        90  PERCENT  OF THE ANALYTE INTO THE 1 MILLILITER,   THAT'S



 13        PRETTY  GOOD RECOVERY,   /^S THE PARTITIONING COEFFICIENT



 14        DROPS DOWN,  SO DOES THE AMOUNT THAT YOU RECOVER,  BUT YOU



 15        CAN SEE,  IF YOU  HAVE GOOD RECOVERY,  YOU GET 90  PERCENT



 16        IN  THE  FIRST MILLILITER;  THAT ESSENTIALLY ALL YOU'RE



 17        DOING AS  YOU CONTINUE TO EXTRACT  IS DILUTE,   NOW,  THIS



 '8        IS  INDICATED BY  THE DASHED  LINES  WHICH SHOW THE CON-



 19        CENTRATION,  So  YOU CAN SEE HERE,  FOR  INSTANCE, THAT



 20        IF  YOU  HAVE GOOD EXTRACTION WITH  1 MILLILITER,  YOU GET



 21        ABOUT 90  PERCENT OF THE SAMPLE IN  THE  WATER,   No  MATTER



 22        HOW MUCH  MORE SOLVENT YOU USE,  YOU CAN ONLY GET 10 PER-



 23        CENT MORE;  THAT'S IT,   NOW,  IF YOU EXTRACT MORE,  BASICALLY



 24        WHAT HAPPENS IS  YOU GET VERY LITTLE MORE OF THE ANALYTE



25        YOU'RE  AFTER, BUT IF YOU'RE LOADED WITH MATERIALS  THAT
                                 10

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 1       DO NOT EXTRACT VERY WELL. YOU WILL EXTRACT MORE  OF



 2       THESE INTERFERENCES,  THIS TENDS TO  SHOW DOWN  HERE,



 3       AND  IT SHOWS A LITTLE BIT BETTER ON  THIS NEXT  GRAPH



 4       WHERE WE ARE SHOWING ONLY CONCENTRATIONS,  NOW,  HERE



 5       AGAIN, I'VE PICKED THREE DIFFERENT PARTITIONING  CO-



 6       EFFICIENTS INDICATING THREE DIFFERENT MATERIALS,  A  IS



 7       QUITE SIMILAR TO MOST OF THE PRIORITY POLLUTANTS; B



 8       WOULD BE SOMETHING LOWER, MAYBE MORE LIKE PHENOL; AND



 9       C WOULD BE SOMETHING THAT'S VERY POORLY EXTRACTED,   IF



10       WE EXTRACT THIS  INTO 1 MILLILITER, YOU CAN SEE THIS  IS



11       MORE OR LESS EQUIVALENT TO THE PEAK  HEIGHT YOU WOULD



12       GET  IF YOU SHOT  EQUIVALENT SHOTS IN  A CHROMATOGRAPH;



13       YOU  WOULD GET A  GOOD RESPONSE TO A,  A SOMEWHAT REDUCED



14       RESPONSE TO B, A VERY LOW RESPONSE TO f,  IF WE



15       EXTRACT THIS INTO 5 MILLILITERS, HERE IS THE RESPONSE



16       WE WOULD GET (INDICATING),  So YOU CAN SEE WE  REALLY



17       HAVE LOST SOMETHING THAT WE'RE REALLY AFTER, AND THAT



18       IS,  THAT BY EXTRACTING WITH A SMALL  VOLUME, WE HAVE,  IN



19       EFFECT, DONE SOME SELECTIVE EXTRACTION, AND THIS IS  ONE



20       OF THE THINGS WE ARE BASICALLY AFTER,  WE GAIN NOTHING



21       BY EXTRACTING A  LOT MORE  IN THE SENSE OF TOTAL RECOVERY,



22       NOW, THEN, THIS  EFFECT WE HAVE NOTICED QUITE FREQUENTLY,



23       FOR  INSTANCE, IN THE EXTRACTION OF PHENOLS, WHERE WE'RE



24       USING THE MORE OR LESS CONVENTIONAL  METHODS, WE  HAVE



25       HAD  PRACTICALLY  NO SUCCESS; WHEN USING THE MICROEXTRACTION
                                   11

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                                        Concentration  ImL vs 5mL
                                           Partition Coefficient
1 ml
5 ml
                                                                                     11A

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1        APPROACH.  ''E  HAVE HAD QUITE GOOD SUCCESS,  PRIMARILY
2        BECAUSE  WE  HAVE A RELATIVELY CLEAN SAMPLE  AS COMPARED
3        TO  EXHAUSTIVE EXTRACTION,  WHICH EXTRACTS MORE OF THE
4        INTERFERING COMPOUNDS,   So, IN A SENSE,  WE CAN USE THE
5       EXTRACTING  PROCEDURE AS A PARTIAL CLEANUP, AND AS A
6       MATTER OF FACT, THAT CAN BE THE CLEANUP,  WE DID NOT
7       USE ANY COLUMN CHROMATOGRAPHY TO CLEAN THE PLANT
8       VERIFICATION SAMPLES,
9         BEFORE I  GET ONTO THE PRACTICAL ASPECTS OF MICRO-
10       EXTRACTION, I WOULD LIKE TO MAKE ONE OTHER OBSERVATION
11       WHICH I THINK MAY HAVE CONSIDERABLE IMPORTANCE DOWN THE
12       ROAD, AND THAT IS, LOOKING AT THIS 1 AND 5 MILLILITER
13       EXTRACTION  AGAIN, YOU WILL NOTICE THAT  IF WE EXTRACT
14       WITH 1 MILLILITER, WE GET A PRETTY GOOD SIGNAL ON Aj
15       THERE'S QUITE A REDUCTION  IN THE SIGNAL FROM A IN THE
16       1 MILLILITER AND A IN THE 5 MILLILITER,   THERE IS LESS
17       OF A REDUCTION IN SIGNAL AS THE PARTITIONING COEFFICIENT
18       BECOMES LESS FAVORABLE,  As A MATTER OF FACT, YOU CAN
19       CALCULATE THE  PARTITIONING COEFFICIENT  WITHOUT EVER
20       KNOWING WHAT THE COMPOUND  IS MERELY BY  MEASURING THE
21       PEAK HEIGHT OF THE 1 MILLILITER EXTRACT AND  THE  5
22       MILLILITER EXTRACT,  NOW,  WE'VE DONE VERY LITTLE OF
23       THIS, BUT  IT DOES LOOK  PROMISING DOWN THE ROAD,   IT
24       WOULD BE VERY  ADVANTAGEOUS TO BE ABLE TO  DETERMINE
25       RECOVERY EFFICIENCIES AT THE LEVEL YOU'RE INTERESTED
                                 12.

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 1       WITH; ACTUALLY WHAT  IS NATURALLY THERE  AND  NO  SPIKING
 2       REQUIRED,  THAT  is NOT THE WAY WE  DETERMINED RECOVERY
 3       DATA FOR THE PLANT VERIFICATION DATA,
 4            THE ACTUAL  MICROEXTRACTION PROCESS IS  REALLY VERY
 5       SIMPLE,  BASICALLY,  THE MECHANICS  ARE,  YOU  TAKE A
 6       100-MILLILITER VOLUMETRIC FLASK, PUT  IN 100 MILLILITERS
 7       OF SAMPLE, PUT IN A  MILLILITER OF  SOLVENT,  SHAKE IT
 8       UP FOR A COUPLE  OF MINUTES,  LET IT STAND UNTIL THE
 9       SOLVENT RISES  INTO THE NECK, AND AS SOON AS THERE'S
 10       ENOUGH THERE TO  GET  INTO A MICROSYRINGE,  YOU CAN
 11       SHOOT  IT,  THAT'S A  LITTLE BIT OF  A SIMPLIFICATION,
 12       BUT THAT'S THE MECHANICS OF  IT, so IN THIS  REGARD,  IT
 13       IS QUITE SIMPLE,
 14            THE DATA THAT WILL BE PRESENTED BY THE OTHER
 15       SPEAKERS WAS OBTAINED FROM PLANT VERIFICATION  STUDIES,
 16       AND AT THAT TIME, THE METHOD WAS MORE OR LESS  BEING
 17       DEVELOPED, BUT BASICALLY, IT COMES DOWN TO  THIS,
 18       IT'S VERY DIFFICULT  TO MEASURE THE SOLVENT  VOLUME
 19       AFTER YOU PUT THE 1  MILLILITER IN,  Do  YOU  GET 1
 20       MILLILITER BACK? WELL, AS A MATTER OF  FACT, MOST OF
 21       THE TIME YOU GET IT  BACK QUITE WELL, ESPECIALLY IN
 22       A SALTED SOLUTION, SO WE GENERALLY SALT,  BUT THERE
 23       ARE TIMES WHEN IT MAY BE ADVANTAGEOUS NOT TO SALT,
 24       THE WAY WE DO IT RIGHT NOW IS TO RUN THE  SAMPLE  AS
25       A DUPLICATE PAIR,  WE TAKE TWO 100-MILLILITER
        VOLUMETRIC FLASKS; WE ADD ABOUT 30 GRAMS  OF SALT
   	12	

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 GENERAL  MICRO-EXTRACT I ON PROCEDURE
I. ADD 50 g HoCI
  TO A 100m\
  VOL. FLASK-
                              O.
     2. ADD 90 «< WATER  SAMPLE,
       INTERNAL STD. AND SPIKE.
   O
3. ADD I •! HEXANE.
     O
     4. STOPPER, SHAKE WELL
       APPROX. t MIN.
  ALLOW PHASES TO
  SEPARATE.
6. SAMPLE WITH 10/-I     7. SAMPLE WITH
  SYRINOE FOR  «C    or   OLASS PlPET
  INJECTION.             AND STORE
                        HEXANE
                        LAYER IN
                        VIAL.
                      13A

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 1       AND 90 MILLILITERS OF THE WASTEWATER TO EACH olf THE
                                                      /
 2       FLASKS,  WE ADD TO EACH FLASK,,,I'M GOING TO CALL  IT
 3       AN INTERNAL STANDARD, AND IT'S GOING TO THROW SOME
 4       OF YOU BECAUSE WE DON'T REALLY USE IT AS AN  INTERNAL
 5       STANDARD,  MAYBE I SHOULD SAY IT AS AN INTERNAL
 6       INDICATOR BECAUSE THE ONLY REASON WE ADD THIS  INTERNAL
 7       INDICATOR IS SO THAT WE CAN NORMALIZE THE DATA,
 8            IF THERE'S ANY DIFFERENCE IN RECOVERED  VOLUMES
 9       OR DIFFERENCES IN SHOOTING, WE CAN COMPENSATE FOR
 10       THIS ON THE BASIS OF THE INTERNAL STANDARD,  IT'S
 H       MERELY A TOOL TO GET AROUND VOLUMETRIC MEASUREMENT
 12       OF THESE VERY SMALL AMOUNTS OF SOLVENT,  NOW, THEN,
 13       IN ONE OF THESE TWO SAMPLES, WE DO ADD A KNOWN AMOUNT
 14       OF THE COMPOUND OF INTEREST, OR COMPOUNDS OF INTEREST,
 15       SO AT THIS POINT IN TIME WE HAVE TWO SAMPLES,  THEY
 16       ARE IDENTICAL IN EVERY RESPECT EXCEPT THAT ONE OF
 17       THEM HAS BEEN DOSED WITH A KNOWN AMOUNT OF MATERIAL.
 18       WE NOW SHAKE THESE FLASKS,  I NOTICE HERE  IT SAYS
 19       ABOUT TWO MINUTESj IT DOES NOT TAKE MUCH AGITATION,
 20       WE AT SOUTHWEST ACTUALLY HAVE A LITTLE ROTATING DEVICE
 21       WHERE WE ROTATE IT AT ABOUT 20 RPM, I THINK  IT IS, AND
 22       LET IT GO FOR ABOUT TEN MINUTES,  IT DOESN'T REALLY
 23       DO IT ANY MORE EFFECTIVELY, BUT EVERY SAMPLE IS
 24       HANDLED THE SAME, ESPECIALLY IN THE PAIR,  THEN THIS
25       PAIR IS ALLOWED TO STAND UNTIL SOLVENT RISES TO THE
                               JA.

-------
1        TOP,   YOU CAN,  AT THIS POINT,  EITHER SHOOT THE SAMPLE
2       OUT OF EACH ONE OR YOU CAN TAKE SOME OF IT OUT, PUT
3       IT IN  A SMALL VIAL AND SAVE IT FOR ANALYSIS LATER,
4       NOW,  IF YOU Q-ET A LITTLE SOLVENT LOSS, IT'S NOT
5       REALLY A BIG DEAL BECAUSE YOU'VE GOT THE INTERNAL
6       STANDARD IN THERE WHICH HELPS YOU IN YOUR CALCULATIONS,
7            NOW, WE HAVE THOSE TWO CHROMATOGRAMS, AND WE
8       ALSO SHOOT A STANDARD SO THAT WE END UP WITH A
9       STANDARD, A SO-CALLED UNSPIKED SAMPLE, AND A SPIKED
10       SAMPLE.  BY THE USE OF THESE EQUATIONS (ESTD, SPIKE-
11       UNSPIKE), WE CAN NOW MAKE THE FOLLOWING CALCULATIONS,
12       THE FIRST ONE, ON THE BASIS OF THE EXTERNAL STANDARD,
13       WE CALCULATE THE MICROGRAMS PER LITER  IN THE UNSPIKED
14       SAMPLE,  NOW, THIS IS JUST A STRAIGHTFORWARD ANALYSIS,
15       AND IT GIVES US AN APPARENT CONCENTRATION  IN MICRO-
16       GRAM PER LITER,  WHAT IS DOES, IT ASSUMES WE PUT  IN
17       1 MILLILITER, THEREFORE WE GOT BACK 1  MILLILITER;  IT
18       ALSO ASSUMES 100 PERCENT EXTRACTION,   IN MANY  CASES,
19       ACTUALLY THIS GIVES QUITE  A GOOD  FIGURE;  IN SOME
20       CASES  IT DOESN'T BECAUSE YOU DO,  IN FACT.  GET  A
21       MATRIX  EFFECT ON CERTAIN SAMPLES; ON  OTHERS THERE IS
22       HARDLY  ANY  MATRIX  EFFECT,  THIS  IS  WHERE  THE  SPIKED,
23       UNSPIKED SAMPLE COMES  IN,  !A'E  CAN NORMALIZE THE  PEAK
24       AREAS,  PEAK HEIGHTS,  WHAT-HAVE-YOU, ON THE UNSPIKED
25       SAMPLE  AND  ON THE  SPIKED SAMPLE,  USING THE INTERNAL

-------
                           CALCULATIONS

     ESTD
 RQ1 X RQ3 X RCW =  6/,
 R02 X R05 X R06
                            R01 =  STANDARD  NG  INJECTED
                            R02 =  AREA OF  INJECTED STANDARD
                            R03 =  AREA OF SAMPLE  INJECTED
                            R04 =  VOLUME OF EXTRACTING SOLVENT  (yL)
                            R05 =  VOLUME OF SAMPLE EXTRACT INJECTED
                                  IN uL
                            R06 =  SAMPLE VOLUME EXTRACTED IN ML
 SPIKE - UNSPIKE
 R16 X R15 .  yG/L
(R13 - R16)
                           Rll = AREA OF UNSPIKED SAMPLE
                           R12 = AREA OF IS IN UNSPIKED SAMPLE
                           R13 = AREA OF SPIKED SAMPLE
                           R14 = AREA OF IS IN SPIKED SAMPLE
                           R15 = yG/L ADDED
                           R16 = CORRECTED AREA OF UNSPIKED SAMPLE
                                ISA

-------
1       STANDARD,  SO THAT THEY ARE EXACTLY ON A COMPARABLE



2       BASIS,   WE NOW, THEN, CAN DETERMINE HOW MUCH IS IN



3       THE UNSPIKED SAMPLE BY THE INCREASE IN THE PEAK



4       HEIGHT OF THE DOSED SAMPLE,  WE KNOW WHAT THAT IS,



5       BUT IT'S ALL AUTOMATICALLY CORRECTED FOR EXTRACTION



6       EFFICIENCY,  So WHEN YOU PROPORTIONATE THE PEAK



7       HEIGHT OF THE UNSPIKED SAMPLE TO THE PEAK HEIGHT OF THE



8       SPIKED SAMPLE LESS THE UNSPIKED SAMPLE, YOU END UP



9       WITH THE ACTUAL MICROGRAMS PER LITER CORRECTED FOR



10       VOLUME LOSSES, CORRECTED FOR EXTRACTED INEFFICIENCIES,



11       AND EVEN CORRECTED FOR DIFFERENT SHOT SIZES,  As YOU



12       CAN SEE, THERE ARE ABSOLUTELY NO VOLUME MEASUREMENTS



13       IN THE CALCULATION (INDICATING),



14            NOW, THEN, WE WANT TO KNOW WHAT OUP RECOVERY



15       IS,  THE WAY WE DID THIS ON A CONSIDERABLE PORTION



16       OF THE VERIFICATION  PROGRAM WAS MERELY DIVIDE THE



17       APPARENT CONCENTRATION THAT YOU FOUND BASED ON



'8       THE EXTERNAL STANDARD BY THE CONCENTRATION DETERMINED



19       ON THE BASIS OF THE  SPIKE-UNSPIKE CALCULATION,



20            ANOTHER WAY YOU CAN DO IT is DETERMINE THE PEAK



21       HEIGHT OR AREA FROM  THE SPIKED SAMPLE AS COMPARED TO



22       AN EXTERNAL  SAMPLE,  THERE ARE A NUMBER OF ADVANTAGES



23       TO MICROEXTRACTION THAT I'VE TRIED TO POINT OUT



24       DURING THIS  TALK,  IN ADDITION, THERE'S A MINIMUM



25       OF GLASSWARE TO CLEAN, WHICH MINIMIZES CONTAMINATION,
                                 16

-------
 1            NOW, THIS IS PARTICULARLY HELPFUL ON PHTHALATES,
 2       WE HAVE HAD MUCH MORE LUCK WITH PHTHALATES WITH
 3       MICROEXTRACTION THAN WITH THE MORE EXHAUSTIVE
 4       EXTRACTION APPROACH,  WE HAVE HAD ESSENTIALLY  NO
 5       EMULSION PROBLEM BECAUSE IT  IS NOT NECESSARY TO
 6       QUANTITATIVELY RECOVER THE SOLVENT,  To BE ABLE TO
 7       GET ENOUGH SOLVENT TO SHOOT, IN MOST CASES, WE
 8       AGITATE SLOWLY SO WE DON'T SEEM TO GET MUCH IN
 9       THE WAY OF EMULSIONS AND SELDOM HAVE TO CONTEND
 10       WITH THEM,  ANOTHER ADVANTAGE is YOU CAN DO THE
 11       VOLATILES AS WELL AS THE SEMIVOLATILES,  THE BIG
 12       ADVANTAGE, PERHAPS, IS THAT  MICROEXTRACTION GIVES A
 13       CLEANER SAMPLE, AND THIS IS  WHAT LETS YOU DO ANALYSES
 14       WHICH ARE OTHERWISE ALMOST IMPOSSIBLE,  ONE OTHER
 15       ASPECT THAT WE LIKE ABOUT IT, BECAUSE WE ARE A
 16       RELATIVELY SMALL LAB, IS ONE PERSON DOES IT,   WHOEVER
 17       OPERATES THE CHROMATOGRAPH IS JUST PREPARING SAMPLES
 18       AND WAITING TO SHOOT THEM, SO IT CAN BE A ONE-MAN
 19       OPERATION VERY EASILY,  THE  FACT THAT  IT'S RAPID
 20       AND UNCOMPLICATED, I THINK,  IS RATHER OBVIOUS,
 21            ANOTHER HELP HERE THAT  WAS POINTED OUT TO ME
 22       THE OTHER DAY, THERE ARE A FAIR NUMBER OF SAMPLES
 23       LOST FOR ONE REASON OR ANOTHER,  IT ONLY TAKES A
24       FEW MINUTES TO OBTAIN ANOTHER EXTRACT,  NOW, THERE
25       ARE SOME MINOR ADVANTAGES,   THERE IS A LOT LESS
                                JLL

-------
1        WASTEWATER TO SHIP AROUND THE COUNTRY, WHICH CAN
2       GET TO BE QUITE A PROBLEM,  IT CERTAINLY USES LESS
3       SOLVENT,  AND AS I WOULD SEE IT DOWN THE ROAD, THE
4       MICROEXTRACTION MAY BE USED AS A POSSIBLE CLEANUP
5       FOR THE MORE POLAR POLLUTANTS THAT PROBABLY WILL BE
6       COMING UP,  IN OTHER WORDS, YOU USE THE MICROEXTRACTION
7       TO GET RID OF THAT WHICH  IS EASILY EXTRACTABLE, AND
8       THEN MACROEXTRACT FOR THOSE MATERIALS WHICH DO NOT
9       EXTRACT VERY EASILY,  To ME, ALL THESE ADVANTAGES ADD
10       UP TO THE FACT THAT YOU CAN JUST GET BETTER DATA WITH
11       MICROEXTRACTION, AND I BELIEVE THIS WILL BE SUBSTANTIATEI
12       BY KATHY AND BILL IN THEIR TALK,  THANK YOU,
13                                 MR, TELLIAPD:  KATHY, DO YOU
14       WANT TO COME UP HERE, AND  I'LL PUT THOSE ON FOR YOU,
15       BEING SIX-FOOT EIGHT LIKE  YOU ARE,
16                                 MS, THRUM:  BILL COWEN AT
17       CATALYTIC ASKED ARTHUR D,  LITTLE,  INCORPORATED, TO
1«       SYSTEMATICALLY EVALUATE THE EFFECTS ON EXTRACTION
19       EFFICIENCY WHEN  USING MICROEXTRACTION,  ALL OF THIS
20       WORK WAS  DONE  IN  A  CLEAN  MATRIX,   BlLL WILL BE TALKING
21       NEXT ABOUT THE RESULTS FROM A WASTEWATER MATRIX,  THE
22       MAJOR OBJECTIVE  OF  THE WORK  I WILL DESCRIBE WAS TO
23       DETERMINE  IF CHANGES  IN THE  SAMPLE TO  SOLVENT  RATIO
24       AFFECTED  THE OBSERVED DISTRIBUTION COEFFICIENT,   ^AY
25       I  HAVE THE FIRST  SLIDE?
                                 JL8_

-------
                                     EVALUATION  OF  MICROEXTRACTION  METHOD
                                     Analytes
                                     Solvent:
                                     Sample:
      00
Benzene

Toluene

Ethyl Benzene

0-Xylene


P entane


Solvent Ratios

   100:1
    20:1
                                     Effects Of:   Salt (Sodium Sulfate)

                                                  Immiscible Organic

                                                  Miscible Organic (CH3CN)
c

-------
 1       VARIOUS EFFECTS ON  EXTRACTION  EFFICIENCIES  WHEN  USING  A
 2       MICROEXTRACTION TECHNIQUE  TO EXTRACT  BENZENE,  TOLUENE,
 3       ETHYL BENZENE, AND  ORTH-Q-XYLENE  FROM CLEAN WATER  INTO
 4       PENTANE WERE STUDIED,  WE  EVALUATED TWO  DIFFERENT
 5       SAMPLE SOLVENT RATIOS:  100 TO 1  AND  20  TO  1,  FURTHER,
 6       WE STUDIED THE EFFECT  OF SATURATING THE  AQUEOUS  ALIQUOT
 7       WITH SALT, AND IN AN ATTEMPT TO IMITATE  POSSIBLE SAMPLE
 8       MATRICES, WE LOOKED AT THE EFFECTS OF ADDING AN
 9       IMMISCIBLE ORGANIC  (CARBON TETRACHLORIDE) TO THE AQUEOUS
10       ALIQUOT AND A MISCIBLE ORGANIC (ACETONITRILE)  TO THE
H       AQUEOUS ALIQUOT,
12           NEXT  SLIDE,  A  MAJOR QUESTION TO  BE  ANSWERED BY THIS
13       WORK WAS  DO YOU REACH  EQUILIBRIUM AT  RELATIVELY  HIGH
14       SAMPLE SOLVENT RATIOS  AND  RELATIVELY  SHORT  EQUILIBRATION
15       TIMES,  TO ANSWER THAT QUESTION WE OBTAINED SOME
16       LITERATURE VALUES FOR  DISTRIBUTION COEFFICIENTS  FOR
17       BENZENE,  TOLUENE, AND  XYLENE,   THAT WORK WAS DONE  BY
is       DELIGNY,  ET AL,,  IN  1966 AND HE EXTRACTED WITH  HEPTANE.
19       FROM THOSE DISTRIBUTION COEFFICIENTS  WE  CALCULATED A
20       PERCENT RECOVERY AT 100 TQ 1 AND 20 TO 1 SAMPLE  TO
21       SOLVENT RATIOS, AND THEN COMPARED THOSE  VALUES WITH-OUR
22       EXPERIMENTALLY DETERMINED  VALUES, As YOU CAN  SEE,
23       THERE'S REASONABLY  GOOD AGREEMENT BETWEEN THE  CALCULATED
24       AND EXPERIMENTAL VALUES, EXCEPT PERHAPS  FOR TOLUENE AND
25       XYLENE AT 100 TO 1, AND THIS COULD BE BECAUSE
        USED HEPTANE, WHILE WE USED  PENTANE.
   	12

-------
                           SINGLE  STAGE  EXTRACTION  EFFICIENCY
                                                 100:1
                                                           20:1
SUBSTANCE
 BENZENE


 TOLUENE


 XYLENE
DISTRIBUTION
 COEFFICIENT
     182
     708


    2818
CALC,
EXPTL,
 65
 96
  66


  82


  89
CALC,
EXPTL,
 90          91


 97         100


 99         100

-------
            AN EXAMINATION OF THE AVERAGE RECOVERIES, PARTICULARLY



1       THOSE FOR BENZENE AT 100 TO 1 SAMPLE TO SOLVENT RATIO



2       INDICATES THAT SUCCESSIVE EXTRACTIONS WERE BEHAVING AS



3       ONE WOULD PREDICT FROM THE THEORY OF MULTIPLE EXTRACTS



4       AND THAT THE DISTRIBUTION COEFFICIENT WAS REMAINING



5       ESSENTIALLY CONSTANT,  BENZENE WAS EXTRACTED AT 66



6       PERCENT AT 100 TO 1  SAMPLE TO SOLVENT RATIO,   IF THE



7       SYSTEM IS AT EQUILIBRIUM, YOU WOULD EXPECT TO REMOVE



8       66 PERCENT OF THE REMAINING 34 PERCENT, OR 22 PERCENT,



9       DURING THE SECOND EXTRACTION,  EXPERIMENTALLY THAT



10       NUMBER WAS 25 PERCENT,  THEREFORE, THE EVIDENCE DOES



H       SUPPORT  THE HYPOTHESIS THAT EQUILIBRIUM  IS REACHED WHEN



12       USING MICROEXTRACTION,  DIFFERENCES BETWEEN THE EXTRAC-



13       TION EFFICIENCIES OBSERVED  IN DUPLICATE EXPERIMENTS WERE



14       QUITE SMALL,  IN MOST CASES, THE  RELATIVE RANGE FOR



15       DUPLICATE  FIRST  EXTRACTIONS WAS LESS THAN 5 PERCENT,



16            NEXT SLIDE,  PLEASE.  THIS BAR GRAPH  PRESENTS  THE



17       DATA, DEMONSTRATING  THE EFFECT OF THE  SAMPLE TO SOLVENT



18       RATIO ON THE  PERCENT RECOVERY OF  BENZENE, TOLUENE,



19       .ETHYL BENZENE AND XYLENE FROM WATER,   THERE WAS NO



20       ADDED ORGANIC MATRIX AND NO  SALT  ADDED IN THESE SAMPLES,



21       AS YOU WOULD  EXPECT, YOU DO  EXTRACT  MORE  AT 20  TO 1



22       THAN AT  100 TO  1 SAMPLE  TO SOLVENT  RATIOS,   FOR  EXAMPLE



23       TOLUENE  WAS ABOUT 100 PERCENT  EXTRACTED  AT 20  TO  1,  AND



24       82 PERCENT AT 100 TO 1.  THE  NUMBERS IN  PARENTHESES  ON



25       THE  BAR  GRAPH ARE THE CALCULATED  VALUES  FOR  THE PERCENT




        RECOVERIES (CALCULATED  FROM  DELIGNY's  DISTRIBUTION




        COEFFICIENT DATA).	2Q  	

-------
                         FIGURE 1
            EFFECT OF SAMPLE  :  SOLVENT  RATIO
         ON PERCENT RECOVERY  OF BTEX FROM WATER
              NO ADDED ORGANIC  MATRIX
                          100
                                         100
                       100
1UU
90
80
70 66
60
50

40
30
20
10
n -
(65)*
rH

O
O
rH




91
(90)*



rH

O
CM




82










(88)*


i— |
• •
o
o
rH
^^




(97)*



^\
!-H

O
CN
\~s















91




/~\
rH

o
o
rH
\^*








s~\
rH

O
CM
*^















89
(96)*



x**^
rH
• •
o
o
rH
*~s




(99)*



s~**
H
0
CM
^




                    Toluene
Ethyl-benzene
o-Xylene
Calculated equilibrium values
                             20A
                                                         Arthur D Little, Inc

-------
            THE NEXT SLIDE.  THIS BAR GRAPH  PRESENTS  THE  DATA
1       FOR EXTRACTING BENZENE AT A  SAMPLE TO  SOLVENT RATIO OF
2       20 TO 1, AND THE EFFECTS OF  ADDING SALT  TO  THE SAMPLE,
3       AS WELL AS THE EFFECTS OF ADDING  3 PARTS PER  MILLION
4       ACETONITRILE, 1,000 PARTS PER MILLION  ACETONITRILE  AND
5       1 PART PER MILLION CARBON TETRACHLORIDE.TO  THE AQUEOUS
6       ALIQUOT,  GENERALLY THE SALT DID  INCREASE THE RECOVERY
7       SOMEWHAT,  FOR A SAMPLE TO SOLVENT RATIO  OF  20 TO  1,  ONLY
8       THE BEHAVIOR OF BENZENE IS SHOWN  BECAUSE RECOVERY OF THE
9       OTHER THREE ANALYTES WAS ESSENTIALLY COMPLETE AFTER  ONE
10       EQUILIBRATION AT THE 20 TO 1 RATIO,  REGARDLESS OF
11       WHETHER ORGANICS OR SALT WERE PRESENT,
12           NEXT SLIDE, PLEASE,  THIS BAR GRAPH  PRESENTS  THE
13       DATA FOR RECOVERY OF BENZENE AT A SAMPLE TO SOLVENT
14       RATIO OF 100 TO 1.  ONCE AGAIN, THE  SALT GENERALLY
15       INCREASED THE RECOVERIES AND THERE DOES  NOT SEEM  TO  BE
16       ANY SIGNIFICANT EFFECT DUE TO ANY OF THE ORGANICS
17       BEING ADDED, EITHER MISCIBLE OR  IMMISCIBLE.
18           NEXT SLIDE, PLEASE,  THIS  IS  THE RECOVERY DATA  FOR
19       TOLUENE AT 100 TO 1.  THERE  IS A  SLIGHT  INCREASE  IN
20       RECOVERY WHEN YOU ADD SALT,  HERE, THOUGH,  I'D LIKE  TO
21       DRAW YOUR ATTENTION TO THE BAR AT 10,000 PARTS PER
22       MILLION ACETONITRILE,  THE RECOVERY  IS SOMEWHAT REDUCED
23       WHEN THERE  IS NO SALT PRESENT,  TOLUENE  WAS EXTRACTED AT
24       78 PERCENT, GIVING AN AVERAGE  OF ABOUT  83 PERCENT FOR THE
25       OTHER BARS,  THAT EFFECT SEEMED TO BE OVERCOME  WHEN SALT
        WAS ADDED, AND THE RECOVERY  WAS  INCREASED TO  93 PERCENT,
                                 21

-------
             FIGURE 2

  EFFECTS OF SALT AND ORGANICS
 ON PERCENT  RECOVERY OF BENZENE
SAMPLE : SOLVENT RATIO 100 : 1
100
90 83 R7
Hz
80
70
60
50
40
30
20
10
n —
74
SSSSS
66














79

65














79

65
















f. O
68
















£. O
68














u
8 ppm 1,000 ppm 10,000 ppm 1 ppm
MeCN MeCN MeCN CC-
-------
           FIGURE 3

EFFECTS  OF SALT AND  ORGANICS
            BENZENE
SAMPLE  :  SOLVENT PATIO 20 :  1
        100
                                 100
1UU
90
80
70
60
50
40
30
20
10
* w
v^^^^^^^>
91















ill
86















93
NXWWW
89















SSSSS
92















8 ppm 1,000 ppm 1 ppm
MeCN MeCN CCJU
N32SOIJ saturated
No
              21B
                                            Arthur D Little

-------
             FIGURE H

 EFFECTS  OF SALT AND ORGANICS
            TOLUENE

SAMPLE  :  SOLVENT RATIO 100  : 1
100
90

on
ou
70
60
50
40
30
20
10


83


82



















93
$S$SS
CvVvVv^Ov
QO
OJ






8ppm
CH3CN












91
^s^v^

85







1000 ppm
CH3CN












93
^§§§§
vN^vvvvv^1
^^VVVVV
78






10,000 pp
CH3CN











m

Ssssx^s

85







1 ppm












  Na2SOit Saturated
  No
             21C
                                             Arthur D Little, Inc

-------
1           FOR ETHYL BENZENE AT  10,000  PARTS  PER MILLION
2       ACETONITRILE THAT EFFECT  IS  MORE STRIKING;  THE
3       RECOVERIES ARE SOMEWHAT LOWER  WHEN  THERE  IS NO SALT
4       ADDED, ELIMINATED WHEN YOU ADD SALT,
5           LAST BUT NOT LEAST, XYLENE,  THAT EFFECT OF
6       ACETONITRILE IS RATHER STRIKING; THE RECOVERY WAS 72
7       PERCENT WHEN 10,000  PARTS PER  MILLION  ACETONITRILE WAS
8       PRESENT VERSUS THE APPROXIMATE AVERAGE OF 90 PERCENT
9       RECOVERY WHEN LOWER  CONCENTRATIONS  OF  OTHER ORGANICS
10       WERE THERE,  THAT RECOVERY WAS SUBSTANTIALLY INCREASED
11       WHEN THE AQUEOUS ALIQUOT  WAS SATURATED WITH SALT AND
12       THE RECOVERY WAS  INCREASED TO  100 PERCENT,
13           IN CONCLUSION, EVEN AT HIGH SAMPLE TO SOLVENT
14       RATIOS, 100 TO 1, OR 20 TO 1,  AND RELATIVELY SHORT
15       EQUILIBRATION TIMES—WE USED TWO MINUTES' WORTH OF
16       SHAKING FOR ALL OF THIS WORK—YOU DO  REACH EQUILIBRIUM,
17       THERE WAS  NO  INCREASE IN  RECOVERY WHEN WE EXTRACTED FOR
18       FIVE OR TEN MINUTES,   SECONDLY,  FOR SPECIES NOT STRONGLY
19       EXTRACTED  FROM THE AQUEOUS  PHASE, SATURATION WITH SALT
20       GENERALLY  INCREASED  RECOVERY,   THERE  IS SOME EVIDENCE
21       THAT WHEN  WATER SOLUBLE ORGANICS ARE  PRESENT IN THE
22       SAMPLE, THE RECOVERY WILL BE DECREASED, AS WE OBSERVED
23       WHEN 10,000 PARTS  PER MILLION ACETONITRILE WERE PRESENT;
24       HOWEVER,  SALT OVERCAME  THAT  EFFECT,  MlCROEXTRACTION, AS
25       JOHN HAS  POINTED  OUT, GENERALLY EXTRACTS LOWER CONCENTRATION!
                                22

-------
                             FIGURE 5
100
 90
 80
 70
 60
 50
 40
 30
 20
 10
 0
91
                  EFFECTS OF  SALT AND ORGANICS
                         ETHYL BENZENE

               SAMPLE :  SOLVENT RATIO 100 :  1
             95
          •^ ^ ^ ^ •^v ^ •*•
             93
96
97
                                      82
                                                           98
                                                  91
         88
                     8 ppm
                     CH3CN
                       1000 ppm
                        CH3CN
         10,000 ppm
           CH3CN
          1 ppm
          CCli,
                      Saturated
                No Na2SOtt
                               22A
                                                             Arthur D Little, Inc

-------
          FIGURE 6
EFFECTS OF SALT AND ORGAN ICS
          O-XYLENE
SAMPLE :  SOLVENT RATIO 100  : 1
100

90

80
/U
60
50
40
30
20
10
n _



89

88


























96
^sJ^J^T
93










8 ppm
CH3CN















97
^NXNNNX
^VVVNXVV
90









l.OOOppr
CH3CN













n 3

J.UU
XV^V^$VN
ooooooo^
§C§XS^
^^
7?







10,000 ppi
CH3CN













n

98
^^^^
Q 0










1 ppm
CC£i+















       saturated
No
            22B

-------
 1       OF NONVOLATILE, WATER SOLUBLE ORGANIC  INTERFERNECES;
 2      THEREFORE, THERE IS LESS SAMPLE CLEANUP  NECESSARY  THAN
 3      YOU WOULD GENERALLY HAVE TO USE WITH AN  EXHAUSTIVE
 4      EXTRACTION,  BASED ON THIS WORK AND SOME OF THE  DATA
 5      THAT BILL IS GOING TO SHOW US, I THINK THAT MICRO-
 6      EXTRACTION CAN  INDEED BE A VERY REPRODUCIBLE  CLEANUP
 7      AND CONCENTRATION STEP, AND WITH THAT, I'D LIKE  TO
 8      TURN IT OVER TO BlLL.
 9                               MR, COHEN:  AT  THIS  POINT IN
 10      TIME, CATALYTIC HAS RECEIVED VERIFICATION DATA FROM
 11       ABOUT 32 ORGANIC CHEMICAL/PLASTICS PLANTS DURING BAT
 12      REVIEW OF THAT  POINT SOURCE CATEGORY FOR EFFLUENT
 13      GUIDELINES DIVISION,  As JOHN HAS ALREADY POINTED  OUT,
 14      THE SAMPLE PREPARATION METHODS AVAILABLE TO US AT  THE
 15      BEGINNING OF THE BAT PROGRAM FOR NONPURGEABLE ORGANICS
 16      WERE EXHAUSTIVE, SEQUENTIAL LIQUID/LIQUID EXTRACTION,
 17       OR IN THE CASE  OF PHENOLS, THE A 26 RESIN EXTRACTION
 18       METHOD, FOLLOWED BY SOLVENT EXTRACTION OF THE RESIN,
 19       THE EXTRACTIONS WERE THEN FOLLOWED BY AN EVAPORATIVE
 20       CONCENTRATION STEP AND SOME SORT OF A CLEANUP, GENERALLY
 21       COLUMN CLEANUP, STEP,  THIS TYPE OF METHODOLOGY  IS
 22       SIMILAR TO THE METHODOLOGY NOW BEING PROPOSED AS OF
 23       THE DECEMBER 3RD FEDERAL REGISTER,
 24            As JOHN HAS TOLD YOU, SOUTHWEST CHOSE TO TRY  THE
25       SINGLE STEP MICROEXTRACTION PROCEDURE USING A SMALL
                                23

-------
 1      QUANTITY OF SOLVENT,  RATHER  THAN  GOING  WITH  THE
 2      EXHAUSTIVE METHODS.   WHAT  I'D  LIKE  TO DO  NOW IS SHOW
 3      YOU SOME OF THE PRECISION  AND  ACCURACY  NUMBERS  THAT
 4      HAVE COME  IN FROM ALL OF THE CONTRACTORS  AND FROM
 5      SOUTHWEST/  TO COMPARE  THE MICROEXTRACTION  METHOD WITH
 6      SOME OF THE OTHER METHODS  THAT WERE AVAILABLE IN OUR
 7      PROGRAM,   THE  QUALITY CONTROL  DATA  WERE COLLECTED
 8      BASICALLY  UNDER THIS  TYPE  OF PROGRAM (SLIDE #1) WHERE  WE HAD
 9      REPLICATE  ANALYSES  ON DAY  ONE,AND ON DAY  TWO AND DAY
10      THREE  WE REQUIRED THAT EACH  SAMPLE  BE SPIKED TO
11      DETERMINE  A SPIKE   RECOVERY,  JOHN  HAS  ALREADY  GONE
12      THROUGH THE METHODOLOGY FOR  CALCULATING PERCENT
13      RECOVERY FROM  MICROEXTRACTION,   FOR THE OTHER
14      METHODS  IT'S JUST THE COMMON METHOD OF  TAKING THE
15      SPIKED SAMPLE  AND THE UNSPIKED SAMPLE AND REFERRING
16      THEM BOTH  TO AN  EXTERNAL STANDARD CURVE AND COMPUTING
17      THE  PERCENT  RECOVERY,
18           THE  ACCURACY  DATA, THEN, ON ALL OF  THESE SLIDES
19      WILL BE  A  PERCENT RECOVERY OF  ADDED SPIKE,  THE
20      REPLICATION  DATA WILL BE IN  TERMS OF THE RELATIVE
21      RANGE; THAT  is,  THE RANGE OF THE TWO DUPLICATES THAT
22      WERE RUN OVER  THE MEAN VALUE  OF THE TWO  DUPLICATES
23       MULTIPLIED BY 100, AND YOU SHOULD NOTE THAT IN THIS
24      METHOD OF  CALCULATION, 200  PERCENT FOR THIS  REPLICATION
25      NUMBER IS  THE  MAXIMUM YOU WILL GET,  I  SHOULD  NOTE
                                 24

-------
                                                      SLIDE #1



                                             ANALYSIS AND QA/QC PROGRAM
          SAMPLE
         	                             <-——• EXTRACT               ANALYZE




                                            ——— EXTRACT ——— ANALYZE
                                                          EXTRACT —————— ANALYZE

            Day
                       2 - SPLIT IN LAB

K5
                                                          HOLD SPIKE            EXTRACT AND ANALYZE
                                                          EXTRACT               ANALYZE

            Day   -    3 - SPLIT IN LAB   /


                                           \              HOLD,  SPIKE           EXTRACT AND ANALYZE

-------
 1       ALSO THAT THESE SAMPLES WERE COLLECTED  FROM A WIDE



 2       VARIETY OF SAMPLE MATRIX TYPES, FROM CLEAN, WELL WATER



 3       FEEDS  INTO THE PLANTS TO THE UNTREATED  PROCESS WATERS,



 4       IN ALL CASES CONVENTIONAL DETECTORS, EITHER FID, EC,



 5       OR SOME OTHER DETECTOR, OTHER THAN MASS  SPECTROMETRY



 6       WERE USED,   IF WE START OUT WITH THE PHENOL METHOD



 7       THAT WAS USED AT THE BEGINNING OF THE PROGRAM, THIS  IS



 8       THE A 26 RESIN, GCFID METHOD,  YOU CAN  SEE FROM THIS



 9       SLIDE  (#2) THAT WE HAVE A WIDE RANGE OF  SPIKE RECOVERIES



10       OVER IN THE  RANGE COLUMN AND WE HAVE A  RELATIVELY HIGH



11       STANDARD DEVIATION OF THE SPIKE RECOVERIES AS



12       COMPARED TO  THE AVERAGE, FOR ALL THE VARIOUS  PHENOLS,



13       IF WE  COMPARE THIS DATA WITH THE MICROEXTRACTION



14       PROCEDURE, WHICH WE  HAVE ARBITRARILY NUMBERED UNDER  OUR



15       SYSTEM #7-5,  I THINK YOU CAN SEE  (SLIDE #3) THAT THERE'S



16       A RELATIVELY LOW STANDARD DEVIATION AND NONE  OF THE



17       VALUES  IN THE RANGE  COLUMN  EXCEED 200  PERCENT RECOVERY,



18       SO THAT WE HAVE A RELATIVELY LOW  VARIANCE OF  OUR  PERCENT



19       RECOVERY OVER ALL THESE SAMPLE TYPES,   OF COURSE,  WE'VE



20       GOT MOST OF  THE DATA FOR PHENOL BECAUSE THAT'S  THE  ONE



21       THAT HAS OCCURRED THE MOST  COMMONLY  IN  THESE  TYPES  OF



22       SAMPLES,



23                               MR,  TAYLOR:   WHAT WAS THAT



24       STANDARD DEVIATION  PERCENT?



25                               MR,  COWEN:   THIS STANDARD
                                    25

-------
                                     SLIDE #2
      Analytical Method I	5_
      Method Description:  A-26 Resin/CC-FID Method
                               SUMMARY  OF SPIKE RECOVERIES  (Revised 12/26/79)
                                   (Percent Recovery)
Compound
Phenol
2 , 4-Dimethy Iphenol
2-Chlorophenol
2 ,4,6-Trichlorophenol
Peaitachlorophenol
2 , 4-Bichlorophenol
2 , 4-Dinitrophenol
4-Mitrophenol
2-Nitrophenol














Average*
46
61
54
101
49
126
24
68
123














Std. Deviation*
46
42
52
49
48
58
_
72
66














Range*
0-250
0-208
0-236
34-200
0-141
63-215
6-42
0-203
13-199














No. of
Samples Spiked
120
42
22
13
18
8
2
10
8














* All Valoec to Percent lecovery of Spikes
                                             25A

-------
                                        SLIDE #3
      Analytical Mtthod f   7-5
                               SUMMARY OP SPIKE UOOVERIES  (Revised 12/26/79)
                                   (Percent Recovery)
      Method Description:   Microextraction with Flp
Coapound
Phenol
4-Chloro-m-cresol
2-Nitro-phenol
A-Nitro-phenol
2,4-Dlnitro-phenol
Pentachlorophenol

















Average*
52
82
53
38
24
34

















Std. Deviation*
14
16
13
17
12
15

















Range*
13-79
54-114
27-71
14-85
2-38
11-55

















No. of
Samples Spiked
53
10
13
11
12
13

















* All Values la Percent Recovery of Spikes 25B

-------
 1       DEVIATION  IS ABSOLUTE,  IN PERCENT  RECOVERY  UNITS,   YOU
 2       TAKE ALL OF THE PERCENT RECOVERY NUMBERS, THAT'S YOUR
 3       PARAMETER, AND THEN YOU CAN GET THE  MEAN  AND THE
 4       STANDARD DEVIATION OF THOSE PERCENT  RECOVERIES,  SO THE
 5       STANDARD DEVIATION REPORTED HERE IS  NOT A PERCENT OF
 6       THE MEAN,  So THE RECOVERY FOR PHENOL  WITH  THIS  METHOD
 7       WAS 52  PERCENT OVER ALL THE SAMPLES  PLUS  OR MINUS 14,
 8        IF YOU  TALK ABOUT ONE STANDARD DEVIATION,
 9            IF  WE  LOOK AT THE INDIVIDUAL SAMPLE RECOVERIES
 10        (SLIDE  #4), WHERE WE ARE NOT LOOKING  AT THE  OVERALL
 11       DATA BASE  FROM ALL THE DIFFERENT TYPES OF SAMPLES,
 12       BUT RATHER WE ARE TAKING ONE TYPE  OF SAMPLE AND
 13       LOOKING AT IT,   I WANTED TO SHOW HERE  THE RECOVERIES
 14       ON DAY  ONE, DAY TWO, AND DAY THREE.  FOR  SAMPLES
 15       WHERE WE HAD AT LEAST TWO AND  IN SOME  CASES THREE
 16       SPIKE   RECOVERIES, ONE CAN SEE WHAT  THE VARIATION
 17       WAS FOR A  GIVEN SAMPLE ON THE THREE  DAYS  OF
 18       VERIFICATION, AND I THINK YOU CAN  SEE  THAT  AT MOST
 19       WE HAVE A  30 PERCENT SPIKE  RECOVERY DIFFERENCE
 20       BETWEEN ANY TWO DAYS,   IF YOU JUST GLANCE AT SOME OF
 21       THE NUMBERS, YOU CAN SEE THAT  IN SOME CASES  THE
 22       AGREEMENT WAS QUITE GOOD,  THIS IS THE SAME SAMPLING
 23       SITE SO THAT THE MATRIX  IS SUPPOSED  TO BE BASICALLY THE
 24       SAME, ALTHOUGH THE CONCENTRATIONS  OF THE  PRIORITY
25       POLLUTANT MAY BE SHIFTING CONSIDERABLY,
                               26

-------
      SLIDE #4


Phenol Spike Recoveries
for Individual Samples
   (Microextraction)

          I Spike Recovery
Sample No.
v_-
i
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Day 1 Day 2
60
53
44
46
42
56
40
66
43
56
37
60
54 66
42 61
39 51
38
37 62
Day 3
58
79
67
75
64
62
67
61
70
64
59
68
58
65
69
54
59
            26A

-------
 1            IF WE LOOK AT  THE  REPLICATION  OF THE
 2       MICROEXTRACTION METHOD,  MOST  OF  OUR DATA ARE ON
 3       PHENOL (SLIDE #5),   WE  HAVE VERY LITTLE DATA ON THE
 4       OTHER PHENOLS AT THIS  TIME.   WE  HAVE AN AVERAGE
 5       RELATIVE RANGE BETWEEN  DUPLICATES  OF 32 PERCENT,
 6       AND  THAT IS  FOR CONCENTRATIONS ABOVE TEN MICROGRAMS
 7       PER  LITER; ALL OF  THESE  REPLICATION SLIDES ARE OF
 8       CONCENTRATIONS ABOVE TEN PARTS PER BILLION UNLESS
 9       NOTES,   I HAVE LISTED  HERE SOME  REPLICATE DATA
10       FROM CONCENTRATIONS  LESS THAN TEN  PARTS PER BILLION
n       SO THAT YOU  COULD  GET  AN IDEA OF THE AGREEMENT THAT
12       WAS  SEEN ON  THESE  SAMPLES, AND ALSO ONE SAMPLE THAT
13       WAS  RUN OF 4-CHLORO-M-CRESOL, SO YOU CAN SEE THAT
14       THE  REPLICATION IS QUITE GOOD, AND BY WAY OF
15       REFERENCE, IF WE LOOK  AT THE  A 26  RESIN METHOD
IB       (SLIDE #6),  THE AVERAGE  is ABOUT 84 PERCENT FOR
17       PHENOL, WHERE MOST OF  OUR DATA LIES,   QUITE A FEW
18       NUMBERS OF 200 PERCENT  RELATIVE  RANGE WERE SEEN,
19            IF WE SWITCH OVER  NOW TO  THE POLYAROMATIC
20       HYDROCARBONS (SLIDE  #7),  THIS PROCEDURE IS BASICALLY
21       EPA  METHOD 610 EXCEPT  THAT IN THIS PROGRAM THE
22       CONTRACTOR DID NOT USE  LIQUID CHROMATOGRAPHY AT THE END,
23       HE USED CAPILLARY  GC WITH FLAME  IONIZATION DETECTION,
24       THE  RESULTS  CAME OUT FAIRLY WELL EXCEPT IN THE CASE OF
25       THE  BENZO (B AND K)  FLUORANTHENESj THE STANDARD DEVIATIONS
                                .2L

-------
                                        SLIDE #5

                             SUMMARY OF REPLICATE ANALYSES
                        (Percent Difference Between  Replicates)

     Analytical Method I    7-5
     Method Description:    Mlcroextractlon u-tt-h Fin
Vj.
Compound
Phenol













4- ch lo ro-m- cres o 1







Average*
32
Phenol Rep 11
Sample
1
2
3
4
5
6
7
8
9


Replicate:
pair







Range*
2-143
:ate Concentrations < 10
Reo *1 r/iB/H
5.6
7.9
5.6
4.9
1.9
0.8
6.9
2.2
l.fi


1.9 ug/1







No. of
Replicate Pairs
13
jg/1
Rep *2 f,,gm
2.2
7.6
5.2
3.2
1.6
1.1
9.7
2.6
1 _R


1.7 ug/1







* All Value* in Absolute Difference Between Replicates, Expressed as Percent of Mean Value
                                          27A

-------
                                      SLIDE  #6
                           SUMMARY OF REPLICATE ANALYSES
                     (Percent Difference Between Replicates)
   Analytical Method I      5
   Method Description:   A-26 Resin/GC-FID Method
Compound
Phenol
2,4-Dimethyl phenol
2,4,6-Trichlorophenol
Pentachlorophenol


















Average*
84
83
75
24


















Range*
17-200
31-153
6-200
9-40


















* Mo. of
Replicate Pairs
21
5
3
2


















All Values In Absolute Difference Between Replicates,  Expressed a* Percent of Mean Value
                                       27B

-------
                                        Table  33
                               SUMMARY OF SPIKE RECOVERIES
                                   (Percent Recovery)
      Analytical Method f   17-4

      Method Description:  EPA Method  610, with Florisil Cleanup, FID Detection
Conpound
Fluoranthene
Pyrene
Phenanthrene
Anthracene
Naphthalene
Acenaphthylene
Fluorene
















Average*
86
72
66
94
36
74
88
















Std. Deviation*
48
36
24
41
17
27
24
















Range*
12-172
13-133
39-1QO
42-161
12-71
31-118
48-113
















No. of
Samples Spiked
9
9
in
Q
12
11
9
















* All Value* la Percent Recovery of Spikes
                                               27C

-------
 1       ARE RELATIVELY LOW COMPARED TO THE  AVERAGES,   NOW,
 2       THIS  IS AN EXHAUSTIVE EXTRACTION  METHOD  SIMILAR TO
 3       THAT  UNDER METHOD 610,  MlCROEXTRACTION  FOR  THESE
 4       KINDS OF  COMPOUNDS  SHOWED VERY LOW STANDARD DEVIATIONS
 5       (SLIDE #8), AND VERY GOOD AVERAGE PERCENT  RECOVERIES
 6       IN THE 80 AND 90  PERCENT RANGE.  YOU  CAN  SEE THE
 7       SMALL RANGE AND STANDARD DEVIATION  FOR THESE KINDS  OF
 8       COMPOUNDS,  THERE WAS AN AWFUL LOT  OF  DATA ON THIS
 9       ONE.  WE  DID NOT, UNFORTUNATELY,  HAVE  AS MUCH DATA
10       ON THE OTHER METHOD (610),  WE HAD  VERY  LITTLE
11       PRECISION DATA ON THE METHOD  610  (SLIDE  #9),
12           GENERALLY THE REPLICATION WAS FAIRLY GOOD; 112
13       WAS THE HIGHEST RELATIVE RANGE VALUE WE  HAD  FOR
14       THIS  METHOD,  To COMPARE THAT WITH  MICROEXTRACTION
15       FOR THESE KINDS OF COMPOUNDS, AGAIN, THERE IS NOT A
16       LOT OF DATA AT THIS TIME, BUT WE  WERE  GETTING VALUES
17       OF AT MOST 24 PERCENT RELATIVE RANGE (SLIDE  #10),
18       FOR CONCENTRATIONS LESS THAN  10 PARTS  PER  BILLION,
19       YOU CAN SEE THE EXCELLENT  AGREEMENT BETWEEN THE TWO
20       DUPLICATES WHEN THEY WERE RUN BY  MICROEXTRACTION,
21           JOHN  MENTIONED SOME OF THE PROBLEMS  WITH
22       PHTHALATES, AND I THINK THIS  SLIDE  (#11) WILL SHOW
23       WHAT  HE WAS TALKING ABOUT,  THIS  IS WHAT USED TO
24       BE CALLED THE FEDERAL REGISTER METHOD, THE PESTICIDE
25       EXTRACTION WITH 15 PERCENT METHYLENE CHLORIDE IN
                                28

-------
                                      SLIDE #8
                             SUMMARY OF SPIKE RECOVERIES
                                (Percent Recovery)
    Analytical Method f
    Method De»cription:   Mi croextraction with FID Detector
Vr
- Compound
Fluoranthene
Fyrene
Phenanthrene
Anthracene
Bena»(a)aatfcract»e
naphthalene
Acenaphthylene
Fluor ene





•









Average*
§5
94
95
97
•7
90
te
92 1















Std. Deviation*
14
14
17
14
22
IS
25
21















Range*
62-121
66-121
49-124
66-126
34-135
46-134
27-130
53-130















No. of
Samples Spiked
24
23
24
24
24
24
24
24















HH1 Value* to t*rc**c Kecovcry •( Spikes 28A

-------
                                      Table 34
                             SUMMARY OF REPLICATE ANALYSES
                       (Percent Difference Between Replicates)

     Analytical Method I    17-4
     Method Description:  EPA Method  610. with Florisil Cleanup. FID Detection
Compound
Fluor an thene
Pyrene
Phenanthrene
Anthracene
Naphthalene
Acenaphthylene
Fluorene















Average*
24
27
42
16
26
29
38















Range*
22-26
6-51
11-110
7-25
10-42
6-73
4-112















No. of
Replicate Pairs
2
3
4
3
4
4
4















* All Values in Absolute Difference Between  Replicates, Expressed as Percent of Mean Value
                                            28B

-------
                                     SLIDE #10


                           SUMMARY OF REPLICATE ANALYSES
                      (Percent  Difference  Between Replicates)
   Analytical Method *
   Method Description:    Mlcroextractton with  FID Detector
^Cotpound
»^-
Fluoranthene
Pyrene
Phenanthrene
Anthracene
Benzo(a)anthracene
Naphthalene
Acenaphthylene
Fluoreae

Compound
Fluoranthene
Pyrene
Pbenanthrene
Anthracene
Renzo (a)anthracen«
Naphthalene
Acenaphthylene
Fluorene




Average*
14
19
12
12
28
16
10
12
Replicate Pa













Range*
-
«»
4-21
-
-
0.6-24
2-18
0.3-23
rs for Concentrations <
Rep. fl (Ug/l)
5.4
9.1
2.4
2.5
-
2.0
6.6
3.4



-
Ho. of
Replicate Pairs
1
1
2
1
1
3
2
2
10 Ug/l
Rep. 12 (ug/1)
4.3
6.9
N.D.
4.0
-
2.0
7.4
N.D.




All Values IB Absolute Difference Between Replicates,  Expressed as Percent of Mean Value
     ND-Not Detected
                                      28C

-------
                                SLIDE #11
Analytical Method I  3-3
                         SUMMARY OF SPIKE RECOVERIES (Revised 12/26/79)
                             (Percent Recovery)
Method Description:  Federal Register Pesticide Extracting- Cleanup with F.r
compound
Bis (2-ethylhexyl) phthalate
Dimethyl phthalate
Die thy 1 phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate


















Average*
56
84
74
66
92


















Std. Deviation*
56
69
65
66
-


















Range*
0-333
0-242
0-236
0-310
86-98


















No. of
Samples Spiked
92
22
20
55
2


















Value* in Percent Recovery of Spikes  28D

-------
1        HEXANE WITH  CLEANUP AND THEN GC/EC DETECTION, AND YOU
2       CAN SEE THAT THE AVERAGE PERCENT RECOVERY AND THE
3       STANDARD DEVIATION ARE SIMILAR OVER ALL OF THE
4       SAMPLE TYPES; THERE WERE MANY SAMPLES WITH BIS
5       (2-ETHYLHEXYL) PHTHALATE AND YOU CAN SEE SOME OF
6       THE RANGES IN THE PERCENT RECOVERY THAT WERE
7       EXPERIENCED DURING THE BAT PROGRAM WITH THIS
8       METHOD,  THE MICROEXTRACTION PROCEDURE (SLIDE #12}
9       SHOWED AT MOST 29 PERCENT FOR THE STANDARD DEVIATION
10       AND AVERAGE RECOVERIES FROM 61 TO 85 PERCENT,  So  IF
11       YOU COMPARE THE STANDARD DEVIATION AND THE AVERAGE AND
12       THEN  LOOK AT THE RANGES, WHICH HAVE A HIGHEST VALUE OF
13       112 PERCENT RECOVERY, YOU CAN SEE THAT QUITE  GOOD
14       RESULTS WERE OBTAINED WITH THIS METHOD OVER,  AGAIN,
15       A  LARGE NUMBER OF SAMPLES FOR THE BEHP COMPOUND,   THE
16       PESTICIDE EXTRACTION, EXHAUSTIVE EXTRACTION  PROCEDURE
17       IN TERMS OF REPLICATION SHOWED SEVERAL 200 PERCENT
is       VALUES  (SLIDE #13), MEANING THAT  IN A LOT OF  THE
19       DUPLICATE ANALYSES  THERE WAS A NUMBER AND A  "NOT
20       DETECTED"; THAT WILL GIVE YOU 200 PERCENT WHEN YOU DO
21       THIS  KIND OF PERCENT RELATIVE RANGE CALCULATION,   YOU
22       CAN SEE AVERAGES OF 110 PERCENT AND W\  PERCENT  FOR  SOME
23       OF THESE REPLICATION ANALYSES,  So THERE WERE PROBLEMS,
24           I  HAVE TRIED TO BREAK DOWN THE SOUTHWEST RESEARCH
25       MICROEXTRACTION DATA  INTO GROUPS  OF GREATER  THAN  10 PARTS
                                  29

-------
                                      SLIDE #12
                                SUMMARY OF SPIKE  RECOVERIES  (Revised 12/26/79)
                                    (Percent  Recovery)
       Analytic*! Method I
       Method Description:   Microextraction with EC Detector
" Coopowod
Bis (2-ethylhexvl)
Phthalate
Bis (n-butyl)phthalate
Bis (n-octyl)phthalate



















Average*
85

61
82



















Std. Deviation*
25

29
21



















Range*
14-118

10-106
36-112



















No. of
Samples Spiked
50

13
13



















* All Values in Percent Recovery  of Spikes
29A

-------
                                    SLIDE #13
                           SUMMARY OF REPLICATE ANALYSES (Revised 12/26/79)
                      (Percent Difference Between Replicates)
   Analytical Method f  3-3
   Method Description: Federal Register Pesticide Extraction, Cleanup'with EC Detector
*"*" Compound
Bis(2-ethylhexyl) phthalate
Dimethyl phthalate
Diethyl phthalate
iVi>n -butyl phthalate
Di-n-octyl phthalate

















Average*
110
58
144
86
_

















Range*
5-200
0-200
0-200
4-200
_

















Mo. of
Replicate Pairs
31
8
6
14
0

















All Values in Absolute Difference Between Replicates,  Expressed as Percent  of Mean Value
                                        29B

-------
 1       PER BILLION AND LESS THAN 10 PARTS  PER  BILLION (SLIDE



 2       #14) SO THAT EACH COMPOUND'S DATA  IS  GROUPED TOGETHER



 3       AND THERE  IS, ADMITTEDLY, VERY  LITTLE DATA ON SOME



 4       OF THESE COMPOUNDS EXCEPT THE BEHP; BUT ONE INTERESTING



 5       THING  IS THAT EVEN AT LESS THAN 10  PARTS PER BILLION,



 6       YOU ONLY HAVE AN AVERAGE VALUE  OF 44  PERCENT FOR THE



 7       REPLICATION, AND IF YOU THINK ABOUT IT,  WITH THIS



 8       METHOD OF  CALCULATING THE RELATIVE  RANGE,  YOU CAN HAVE



 9       TWO DUPLICATE ANALYSES OF THE SAME  SAMPLE  IN WHICH



10       ONE IS ONE PART PER BILLION AND THE OTHER  ONE IS TWO



1!       PARTS  PER  BILLION AND THIS TYPE OF  ANALYSIS WILL GIVE



12       YOU A  VALUE OF 67 PERCENT FOR THE RELATIVE RANGE,



13       SO WE  ARE  NOT TALKING ABOUT VERY MANY MICROGRAMS PER



14       LITER  WHEN WE ARE DOWN AT THIS  RANGE,



15           FINALLY, I WOULD LIKE TO SHOW SOME  DATA THAT HAS



16       SOMETHING  TO DO WITH WHAT KATHY WAS TALKING ABOUT,   THE



17       OTHER  MAJOR GROUP OF COMPOUNDS  RUN WITH MICROEXTRACTION



is       BY SOUTHWEST WAS THE NONCHLORINATED VOAs,  THE BENZENE,



19       TOLUENE, ETHYL BENZENE GROUP, AND THERE IS A LOT OF



20       SAMPLES IN THIS GROUP AND YOU CAN SEE (SLIDE #15)  THAT



21       THE AVERAGE RECOVERIES ARE QUITE HIGH AND  THE STANDARD



22       DEVIATIONS ARE QUITE LOW RELATIVE TO  THE AVERAGES,



23       IF YOU REMEMBER KATHY'S SLIDE,  WHEN YOU TAKE INTO



24       CONSIDERATION THE STANDARD DEVIATION  OF THE SPIKE



25       RECOVERY,  WE ARE TALKING ABOUT  THE  SAME RECOVERY RANGE
                                  30

-------
                                   SLIDE #14
                           SUMMARY OF REPLICATE ANALYSES (Revised  12/26/79
                      (Percent Difference Between Replicates)
   Analytical Method I   7-4
   Mftbod Description:   Microextraction with  EC  Detector
VI-
Compound
Bis(2-ethylhexyl)
phthalate (Cone. >10 yg/1)

Si R (?_c.fhyl He*y 1 •>
phthalate (Cooc. <10 Kg/1)

Hi R fn-hiit-yl 'kphfhfll fltP
(Cone. >10 Ug/1)

M c (n— hiityl^phthf»l atp
(Cone. <10 yg/1)

Bis (n-octyl)phthalate
(Cone. >10 y«g/l)

HI e (n—fir-t-vl )nhtIKji1 At"»
(Cone. <10 yg/1)



<

Awrete*
26


44


21


36


29


20






Range*
0-74


0-148


9-28


0-67


-


0-11






Mo. of
Replicate Pairs
5


20


3


8


1


7






All Valwec §• ***l«ee Mfference Between R«plicate>.  Expressed  as  Percent of Mean Value
                                         30A

-------
                                         SLIDE  #15
                               SUMMARY OF SPIKE RECOVERIES (Revised 12/26/79)
                                   (Percent Recovery)
      Analytical Method f   7-1  7.1
      Method Description:     Microextraction with FID Detector	
^fmimtmif

Benzene
Toluene
Ethylbenzene




















Average*
101
95
93




















Std. Deviation*
19
17
17




















Range*
50-160
53-153
32-130




















No. of
Samples Spiked
62
86
49




















* All Value* i» Percent Recovery of  Spike*  30B

-------
1       THAT SHE FOUND WITH HER  CLEAN  WATER  STUDIES;  IN  OTHER
2       WORDS, ABOUT 85 TO 100 PERCENT SPIKE RECOVERIES,
3       FINALLY, REPLICATION  FOR THESE TYPES OF  COMPOUNDS
4       SHOWED THESE AVERAGES, 31 DOWN TO  7  PERCENT  FOR
5       THESE COMPOUNDS BY MICROEXTRACTION (SLIDE  #16),
6       AT THIS POINT,  I WILL OPEN IT  UP TO  QUESTIONS  TO
7       EITHER MYSELF, JOHN OR KATHY,   H'OW MUCH  TIME  DO  WE
8       HAVE LEFT, BlLL?
9                                  MR,  TELLIARD:   IF  YOU  HAVE
10       ANY QUESTIONS, WOULD  YOU GO TO ONE OF THE  MIKES  AND
11       IDENTIFY YOURSELF  SO  WE  CAN FOREVER  BLAME  YOU,
12                                  MR,  SPRAGGINS:   BOB SPRAGGINS,
13       RADIAN CORPORATION,   I HAVE SEVERAL  QUESTIONS, BUT THEY
14       ARE REAL SHORT,  ONE, HOW DO YOU  EXPLAIN THE  FACT  THAT
15       CLASSICALLY  IN  CHEMISTRY WE ARE TOLD THAT  ABOUT  THREE
16       EXTRACTIONS  ARE NECESSARY; I KNOW  THE EXTRACTION
17       COEFFICIENT  HAS SOMETHING TO DO WITH IT,   HOW DO YOU
18       EXPLAIN THAT YOU ARE  GETTING SUCH  GOOD RESULTS WITH ONE?
19       HOW DO YOU EXPLAIN THIS  BUSINESS  ABOUT THE CALCULATION?
20       I  HAD A LITTLE  TROUBLE GOING THROUGH THE CALCULATIONS,
21       YOU WERE SAYING THE  SPIKED MINUS  THE UNSPIKED AND  IT
22       LOOKS LIKE THAT THERE IS A FRACTION  OF THE SPIKE THAT IS
23       NOT GOING TO BE RECOVERED,  IT DOES  NOT LOOK LIKE  IT IS
24       A  REAL STRAIGHTFORWARD EQUATION,  JUST LIKE ONE,  A  MINUS
25       B, SO  I WOULD  LIKE TO HAVE SOME HELP THERE.   THE THIRD
                                31

-------
                                      SLIDE #16
                             SUMMARY OF REPLICATE ANALYSES
                        (Percent Difference Between Replicates)

     Analytical Method f    7-1.3
     Method Description:    Microextraction with Fin n»i-«»rt-nr—
v^
Compound
Benzene
Toluene
Ethylbenzene



















Average*
7
12
31



















Range*
1-36
0-92
0-200









•









Mo. of
Replicate Pairs
16
28
11



















* All Valite* is *sol«t« Difference Between Replicates. Expressed as Percent of Mean V«l««
                                         31A

-------
1       QUESTION WAS,  HOW ARE YOU ADDING YOUR SPIKES IN?  IF
2       YOU'RE ADDING  IT IN AN ORGANIC SOLVENT, IT SEEMS LIKE
3      THIS ORGANIC SOLVENT COULD BE PLAYING SOME EFFECT
4      AND YOU DIDN'T MENTION EXACTLY HOW THAT WAS BEING DONE.
5                                MR, RHOADES: YES, I'LL TAKE
6      THAT BACK,  I'VE HIT THIS PRETTY FAST SO THERE ARE
7      SOME LITTLE DETAILS THAT WE PROBABLY HAVE MISSED THAT
8      REALLY SHOULD BE IN THE METHOD.  YOUR FIRST QUESTION
9      WAS WHY DO WE GET GOOD RECOVERY ON THE MICROEXTRACTION
10      AS COMPARED TO THE EXHAUSTIVE EXTRACTION THAT HAS BEEN
11      USED FOR YEARS,  WELL, I'M PRETTY OLD, BUT THEY STARTED
12      THE EXHAUSTIVE EXTRACTION BEFORE  I REALLY GOT INTO
13      THIS, SO  I'M NOT  SURE  THAT I CAN ANSWER THAT, OTHER  THAN
14      TO  SAY  THIS:  ONE OF  THE BIGGEST  ADVANTAGES OF THE
15      MULTIPLE  EXTRACTION  AND THE EXHAUSTIVE EXTRACTION  IS
16      YOU CAN'T  GET  IT ALL OUT EACH TIME.   IN OTHER WORDS,  IF
17      FOR  INSTANCE, YOU EXTRACT, SAY, A  LITER  OF WATER WITH
18      60  MILLILITERS OF,,,I'LL PULL  IT  OUT  OF A  HAT, DCM,
19      YOU WILL,  IN FACT,  GET A VERY  GOOD RECOVERY,  THE
20      PROBLEM COMES  IN, YOU DON'T  USUALLY  GET  IT  ALL OUT, SO
21      YOU GET OUT, NOW YOU ADD AGAIN, NOW  YOU'VE  DILUTED,
22      SO  YOU  APPROACH  100 PERCENT  BY  DILUTING AND EXTRACTING
23      OUT,  FOR ALL  PRACTICAL PURPOSES,  IT  WAS  ALL IN  THE
24      FIRST EXTRACTION;  WHAT YOU  LEFT BEHIND WAS THE  VOLUME
25      OF  DC7I THAT YOU  LEFT BEHIND,   NOW,  THE ONLY REASON I
                                  32

-------
 1      CAN SAY THAT  IS, THERE'S NOTHING.,,THE  CALCULATIONS
 2      HERE, THE  INITIAL ONES, ARE  QUITE  STRAIGHTFORWARD
 3      AND INDICATE  THAT IF YOU HAVE  A MATERIAL THAT
 4      PARTITIONS, L:ET'S SAY, SOMETHING  IN  THE RANGE OF 1,000
 5      TO 1  TO 10,000 TO 1, WHICH  IS  WHAT MANY OF THESE
 6      ARE, THE MATHEMATICS SHOW THAT YOU SHOULD GET GOOD
 7      EXTRACTION, THE RESULTS SHOW THAT  YOU DO GET GOOD
 8      EXTRACTIONS,  THAT'S ALL I  CAN SAY,
 9                                MR,  SPRAGGINS:   You HAVE ME
10      AT A SLIGHT DISADVANTAGE, BUT  ON THE CALCULATIONS, IF
11      YOU'RE GETTING CLOSE TO 100  PERCENT RECOVERY, I AGREE
12      THAT IT'S  A MINUS B, BUT IF  YOU'RE NOT  GETTING 100
13      PERCENT RECOVERY, WHICH  IT MAY  BE  IN A REAL WORLD SAMPLE,
14      IT LOOKS LIKE THE CALCULATIONS ARE A BIT MORE
15      COMPLICATED,  BUT I'LL HAVE  TO  GO BACK AND LOOK,
is                                fIR, RHOADES:   IF YOU DEVELOP
17      THE FORMULA,  REALLY, THE FACT  THAT YOU  DON'T GET FULL
18      EXTRACTION, IT WILL SHOW UP,  IF YOU USE A LESS
19      EFFICIENT  OR  THE PARTITIONING  COEFFICIENT DOES NOT
20      FAVOR AS GOOD EXTRACTION, MATHEMATICALLY YOU'RE  STILL
21      IN JUST AS GOOD A SHAPE,  YOU  KNOW THAT YOU HAVE
22      NOT EXTRACTED ALL OF IT SO  YOU CAN CORRECT ITj THAT'S
23      ALL I,,,NOW,  I THINK THAT ANSWERS  THAT  ONE,
24          Now, I'M  SURE THERE'S A  LOT BETTER  MATHEMATICIANS,
25      IN THIS ROOM  THAN I AM, BUT  IF YOU ACCEPT THE FIRST
                                33

-------
1       EQUATION,WHICH I THINK IS DIFFICULT TO ARGUE WITH, THE
2       TOTAL IS THE SUM OF THE PARTS  IS WHAT THAT SAYS, THEN
3      THE REST OF THAT IS JUST STRAIGHTFORWARD MATHEMATICS,
4      AND THIS IS THE FORMULA THAT WE DEVELOPED THE CURVES
5      FROM,AND ALL I CAN SAY HERE IS THAT THIS 'IS JUST A PURE
6      MATHEMATICAL ANALYSIS BASED ON THAT FIRST SUPPOSITION,
7      AND I DON'T ARGUE WITH ANYBODY FOR NOT BELIEVING THIS
8      BECAUSE  I FIND IT KIND OF DIFFICULT MYSELF, BUT  I HAVE
9      ACTUALLY DONE SOME OF THIS 1 AND 5, IT GOES JUST
10      EXACTLY BY THE MATHEMATICS,
11                                MS, THRUN:  JUST TO HELP OUT
12      THAT A LITTLE BIT,  THE WORK THAT WE DID AT A.D.L,,  WE
13      USED AN  EXTERNAL STANDARD CURVE FOR ALL THOSE PERCENT
14      RECOVERIES THAT DID AGREE WITH THE PARTITION
15      COEFFICIENT LITERATURE VALUES,  WE DIDN'T USE JOHN'S
16      EQUATIONS WITH THE INTERNAL STANDARD; THAT'S WHY YOU
17      SAW A FIGURE FOR XYLENE AS WELL AS THE OTHER THREE
18      ANALYTES,  DlD EVERYBODY HEAR THAT?
19                                MR, TELLIARD:  No,
20                                MS. THRUN:  SORRY ABOUT THAT,
21      THE WORK THAT WE DID AT A,D, LITTLE, WITH THE CLEAN
22      MATRIX, WE DIDN'T USE JOHN'S EQUATION, WE USED A
23      STRAIGHTFORWARD FOUR POINT CALIBRATION CURVE;THEREFORE,
24      THOSE EQUATIONS WEREN'T USED,  THE PARTITION
25      COEFFICIENT, IN THE LITERATURE, WHEN YOU CALCULATED  A
                                  34

-------
 1       PERCENT RECOVERY, THAT AGREED  VERY  NICELY WITH THE

 2       EXPERIMENTAL VALUE; JUST AN ADDED  POINT,
 3                                FIR,  RHOADES;   I'LL THROW

 4       THIS  IN,   I THINK  THAT WHAT'S  HAPPENED  IS THAT MANY

 5       OF THESE THINGS, THEY ARE EXTREMELY  EASY TO EXTRACT

 6       AND THIS HAS NOT BEEN REALIZED BY  MOST  PEOPLE,   THE

 7       MATRIX EFFECTS MAY OR MAY NOT  BE OVEREMPHASIZED,

 8       THIS  ONE DOES DEPEND LARGELY  ON THE  COMPOUND.   FOR

 9        MANY OF  THESE,  I'LL SAY THE PURE  HYDROCARBON TYPE;
10       THEY  APPARENTLY EXTRACT QUITE  WELL WITHOUT SALTING

11       IN MANY INSTANCES OR ANYTHING  ELSE.   As YOU GET INTO

12       THE MORE WATER SOLUBLES, FOR  INSTANCE,  PHENOLS,  YOU
13       START TO HAVE TROUBLES. NITROBENZENE, IF  YOU DON'T

14       SALT  THAT;  YOU DON'T GET MUCH BACKJ IF YOU SALT IT, YOU

15       DO,   NOW,  THERE ARE SOME STRANGE THINGS HERE AND  I'LL

16       THROW OUT  SOME NUMBERS; UNFORTUNATELY, THEY'RE

17       RECORDING  THIS, BUT USING THE  EXHAUSTIVE  EXTRACTION
18
        APPROACH FOR PHENOLS FROM CLEAN WATER,IT  IS MY

19       UNDERSTANDING FROM THE WORK WE HAVE  DONE  AND I  BELIEVE
20
        WORK  OTHERS HAVE DONE THAT THE EXTRACTION EFFICIENCY

21       RUNS  AROUND 40 TO 45 PERCENT,   NOW,  THIS  IS WITH  THE

22       REGULAR PROCEDURE OF AN ACID, OR A  BASE  CLEANUP  AND

23       THEN  AN ACID EXTRACTION TYPE OF THING USING, WELL,I
24
25
GUESS IT'S DCFI IN THAT PROCEDURE.  Now, THEN, WE MOSTLY
USE HEXANE; YOU'LL BE SURPRISED WHAT GOES  INTO  HEXANE,
                                 35

-------
1          EVERYBODY SAYS IT'S NOT POLAR ENOUGH,  WELL, ALL
2      I CAN SAY ISj TRY IT,  IT DOES DO AMAZINGLY WELL,
3      BUT IT DOESN'T DO EVERYTHING,  WE USED DI(ISOPROPYL)
4      ETHER TO EXTRACT THE PHENOL AND NOW YOU'RE NOT GOING
5      TO BELIEVE ME,  WE GET 70 PERCENT OF THE  PHENOL
6      INTO THE 1 MILLILITER OF WATER; THE EXHAUSTIVE
7      EXTRACTION GETS 40 PERCENT,   IT SHOWS THE DIFFERENCE
3      OF THE SALTING,
a                                 MR, PATERSON:  DI(ISOPROPYL)
10      ETHER?
11                                MR,  RHOADES:  Di(ISOPROPYL)
12      ETHER, YES,  THE REASON WE USE DI(ISOPROPYL)  ETHER  IS
13      BECAUSE  IT HAS LOW WATER SOLUBILITY AND  IT HAPPENS
14      TO BE.,,WELL  TO EXTRACT,  IT HAS  PEROXIDES PROBLEM
1*      BUT HERE, AGAIN, REMEMBER, WE'RE  USING 1  MILLILITER.
16      WE BUY TREMENDOUS STOCKS OF THIS, WE BUY  IT 500
17      MILLILITERS  AT A TIME-QR SOMETHING LIKE  THAT,
18                                MR,  HENDERSON:   I'M JIM
19      HENDERSON WITH CARBORUNDUM,   I'D  JUST LIKE TO SUGGEST
20      THAT SOMETIMES IN THE EXHAUSTIVE  EXTRACTION PROCEDURES,
21      YOU'RE NOW LOOKING AT TWO FACTORS; THAT  is, THE
??      EXTRACTION RECOVERY  AS WELL AS THE LOSSES FROM
23      CONCENTRATION,  I DON'T KNOW  WHETHER YOU'RE MEASURING
24      THE RECOVERY WITHOUT A CONCENTRATION STEP, BUT
25      YOUR VALUES MAY BE CLOSER  IN  COMPARING YOUR MICRO-
                                36

-------
 1      EXTRACTION PROCEDURE WITH AN EXTRACTION  WITH  NO
 2      CONCENTRATION STEP, IF YOU'RE JUST  INTERESTED IN
 3      THE PHENOMENON OF RECOVERY EFFICIENCY,
 4                                MR. RHOADES:   WELL,  THIS
 5      IS TRUE DEPENDING, REALLY, ON THE VOLATILITY  OF THE
 6      COMPOUNDS, WE HAVE HAD, FOR  INSTANCE,  IN PESTICIDES
 7      AND PHTHALATES AND MANY OF THESE OTHERS,  KuDERNA-
 8      DANISH  is EXTREMELY EFFICIENT,  Now,EVENTUALLY YOU
 9      GET DOWN TO THE POINT, FOR INSTANCE, YOU  COULDN'T
10      DO BENZENE BY EXHAUSTIVE EXTRACTION  AND  GO  THROUGH
„      A KUDERNA-DANISH, BUT  IT WORKS VERY  WELL,   I  HAVE
12      NO COMPLAINTS ON THE EFFECTIVENESS OF  KuDERNA-DANISH,
13                                MR, HENDERSON;   I NEED
14      SOME CLARIFICATION ON  SOME OF KATHY'S  DATA,   DlD  YOU
15      INDICATE THAT THE ADDITION OF ONE PART PER  MILLION
16      OF CARBON TETRACHLORIDE TO THE WATER INCREASES THE
17      RECOVERY EFFICIENCY?
is                                MS, THRUM:   A  SIGNIFICANT
19      EVENT FROM CARBON TETRACHLORIDE.  THE  ONLY  EFFECT
20      FROM ORGAN ICS THAT WE  COULD SEE WAS  WHEN  YOU  ADDED
21      10,000  PARTS PER MILLION OF ACETONITRILEj
22      THEN YOU REDUCE THE RECOVERY,
23                                MR, HENDERSON:  THAT WAS
24      A REDUCTION,
25                                MS, THRUM:   IT  REDUCED  IT,
                                 37

-------
1      AND THEN WHEN YOU ADDED  SALT, YOU  OVERCAME  THAT EFFECT,
2                                 MR,  HENDERSON:   I  STAND
3      CORRECTED,
4                                 MR,  RHOADES:  I DID NOT ANSWER
5      ONE OTHER QUESTION THE GENTLEMAN  HAD  OVER  HERE,  HOW
6      DO WE SPIKE,  GENERALLY,  IN  ACETONE WE  MAKE  UP
7      SPIKING SOLUTIONS,   WE GENERALLY  SPIKE  LESS  THAN 100
8      MICROLITERS, IN  10 TO 100 MICROLITERS,   FREQUENTLY,
9      IF WE'RE GOING  TO GO UP  TO 100 MICROUTIRS,WE THEN  PUT
10      100 MICROLITERS OF ACETONE UNDER  THE  lUNSPIKED SAMPLE,
11      ALSOj BUT BASICALLY  WE TRY TO GET EVERYTHING TO CANCEL
12      OUT,
13                                 MS,  THRUN:  JUST TO TAKE
14      THAT ONE STEP FURTHER, WHEN  WE WERE SPIKING,WE SPIKED
15      IT NEAT, IT WASN'T  IN ANY SOLVENT; WITH  MUCH  DIFFICULTY,
16      BUT WE  SPIKED  IT IN,
17                                 MR,  BLOOfli  SAUL BLOOM, EXXON
18      RESEARCH.   THE  QUESTION  I HAVE is, OF  THE DATA THAT  WE'VE
'9      SEEN PRESENTED  THIS  MORNING,  WERE THE:SI ON REAL WORLD
20      SAMPLES OR  JUST ON BLENDS IN WATER?
21                                 MS,  THRU;  TWE  DATA THAT I
22      PRESENTED WAS ALL ON CLEAN WATER,  DION1ZED DISTILLED
23      WATER,  THE DATA THAT BlLL PRESENTED  WAS OUT OF SAMPLES
24      COLLECTED FOR THE ORGAN ICS PLASTICS  INDUSTRY AND THEY
25      REPRESENTED VERY REAL SAMPLES,
                                  38

-------
 !                                 MR,  WALLIN:   BRUCE WALLIN,
 2       E,C,  JORDAN  COMPANY,   THIS is  A COMMENT,  NOT  A  QUESTION,
 3       IN  JUNE   '79 AN  ARTICLE  WAS  PUBLISHED  IN THE JOURNAL
 4       OF  AMERICAN  WATERWORKS  ASSOCIATION ON A,,,MAYBE WE
 5       CAN CALL IT  A SEMI-MICROEXTRACTION PROCEDURE USING
 6       SINGLE STEP,  5 PERCENT,  SOLVENT VOLUME,AND THEY FOUND,
 7       LOOKING  AT TRIHALOMETHANES IN  PARTICULAR,THAT THE
 8       PROCEDURE AGREED VERY  WELL WITH THEORY,   SlNCE THEN
 9       WE'VE BEEN TRYING IT WITH  SOME MORE REAL WORLD
10       SAMPLES,  OF COURSE, THEY  USE  A CLEAN  MATRIX IN THEIR
11       TEST, AND WE'RE ENCOURAGED  WITH THE DATA THAT WE'RE
12       GETTING, BUT IT'S MUCH TOO SOON TO SAY ANYTHING ABOUT
13       THAT, EXCEPT THAT WE ARE ENCOURAGED,
14                                 MS,  THRUN:   YES, THERE WAS
15       ALSO A RECENT PAPER  IN THE JOURNAL OF  CHROMATOGRAPHY
i6       BY  MURRAY, WHO USED,  I  BELIEVE,  20,000  TO 1 SAMPLE TO
17       SOLVENT  RATIOS, AND HE  WAS  GETTING REASONABLE RECOVERIES
18       FOR THE  PESTICIDES; AND I THINK HE ALSO LOOKED AT
19       PHTHALATES AND SOME HYDROCARBONS;  SO THERE IS MORE AND
20       MORE  SUPPORT OF  DATA OUT THERE.
21                                 MR, ENGELSKIRCHEN:   I'M  TODD
22      ENGELSKIRCHEN FROM NALCO CHEMICAL COMPANY,  WE HAVE USED
23       THIS  KIND OF  PROCEDURE TO  LOOK AT PRODUCT SAMPLES FOR
24       TRACE MONOMERS, FOR EXAMPLE,   WE DILUTE THE PRODUCT
25       APPROXIMATELY 1  IN 5 AND THEN  DO A MACROMICROEXTRACTION.
                                  39

-------
 1       OUR  SOLVENT TO DILUTION RATIOS ARE MUCH HIGHER AND WE
 2       HAVE MEASURED EXTRACTION EFFICIENCIES OVER 90 PERCENT
 3       BY SPIKING; WE USE SERUM VIALS BY SPIKING THROUGH THE
 4       SEPTUM WITH A CONCENTRATED SOLUTION,   WE GET AROUND
 5       A LOT OF MECHANICAL PROBLEMS; WE CAN DETERMINE
 6       EXTRACTION EFFICIENCIES ON THE SAMPLES ONE AT A TIME,
 7       EVERY SAMPLE HAS ITS OWN EXTRACTION EFFICIENCY DONE
 8       ON THE SAME VIAL, AND WE CONSISTENTLY GET OVER 90 PERCENT
 9       FOR SOME THINGS THAT YOU WOULD NOT BE ABLE TO DO WITH
•10       THE STANDARD EXTRACTION PROCEDURE BECAUSE THE MATERIAL
 11       ITSELF IS TOO VOLATILE, I THINK; IN OUR HANDS, I
 12       HAVE NO DATA WITH ME, BUT IN OUR HANDS, IT's WORKED WELL,
 13                                 MR. OLLISON:  WILL OLLISON,
 14       A.P.I,  A BRIEF COMMENT TO THE FIRST SPEAKER,  YOU
 15       MENTIONED ONE OF THE THINGS THE APPROACH WAS DEPENDENT
 16       UPON WAS THAT THE PARTITIONING COEFFICIENT MUST REMAIN
 17       CONSTANT OVER THE RANGE OF INTEREST; THAT'S THE RANGE
 18       OF VOLUME YOU'RE USING?
 19                                 MR, RHOADES:  No,  THE RANGE
 20       THAT I'M TALKING ABOUT  IS THE CONCENTRATION RANGE OF
 21       THE MATERIAL OF INTEREST,  IN OTHER WORDS,  IF WE ARE
 22       WORKING AT SOMETHING LIKE 10 PARTS PER BILLION, WE DO
 23       NOT SPIKE, THEN, AT 10 PARTS PER MILLION, WE WILL SPIKE
 24       AT.,,AND  I HAVE SOME DISAGREEMENT WITH MY  COHORTS
 25       HERE,   I DO NOT LIKE TO SPIKE AT; SAY, TWICE  THE LEVEL;
                                 40

-------
 1      EXPERIMENTAL ACCURACY  IS  NOT  GOOD  ENOUGH TO SUBTRACT
 2      A PEAK THAT BIG FROM ONE  THAT BIG,   So I ARBITRARILY
 3      HAVE PICKED A  FACTOR OF 7,  THIS GIVES YOU FAIRLY
 4      BIG  IF YOU'VE  GOT A GOOD  RECOVERY,  BUT IN THINGS LIKE
 5      PHENOL IT'S NOT THAT MUCH MORE; SO  YOU DON'T HAVE
 6      AS MANY RERUNS,AND  IN  MY  OPINION, THIS  GIVES BETTER
 7      DATA, BUT  IT EXPANDS..,IT'S LESS THAN  A FACTOR  OF 10 IN
 8      CONCENTRATION,
 9                                MR,  OILISON:   You MENTIONED
10      ALSO THAT  SALTING OUT  OCCASIONALLY  WAS A PROBLEM,
11      ADDING SODIUM  CHLORIDE WAS A  PROBLEM,IN SOME SITUATIONS.
12      WHEN is THIS A PROBLEM?
13                                11R.RHOADES:   No,  I'M  AFRAID
14      I MISINFORMED  YOU THERE.  THERE ARE SOME INSTANCES WHERE
15      YOU DO NOT NEED TO ADD SODIUM CHLORIDE.   NOW, MOST OF
16      THE PHTHALATE  DATA THAT YOU SAW PRESENTED HERE  BY
17      BILL COWEN WAS NOT SALTED,  THE REASON HERE is, IN OUR
18      HANDS, MAYBE WE'VE GOT A  MESSY LAB,  I  DON'T KNOW; THE
19      FEWER THINGS THAT COME IN CONTACT WITH A SAMPLE THAT
20      YOU'RE DOING PHTHALATES, THE LESS PHTHALATES YOU FIND,
21                                FIR,  OLLISON:   A THIRD QUESTION
22      WAS, IN ANY OF THE SAMPLES IN THESE STUDIES THAT HAVE
23      BEEN REPORTED, WERE THERE  APPRECIABLE  LEVELS OF PARTICULATE
24      MATTER AND DID THIS CONSTITUTE A PROBLEM IN THE TIME
25      YOU EXTRACTED  IT?
                                  41

-------
i                                 MR, RHOADES:   MOST  OF  THE
2      SAMPLES WERE WHAT  I  WILL  CALL TRULY AQUEOUS SAMPLES,
3      AND  I WILL MAKE  NO CLAIMS WHATSOEVER WHEN YOU GET TO
4      A THREE-PHASE  SYSTEM,
5                                 MR, OLLISON:   THE FINAL
6      QUESTION WOULD BE, DO  YOU RECOMMEND THIS AS A
7      REPLACEMENT  FOR  THE  SPARGING METHOD FOR THE VOLATILES?
8                                 MR,  RHOADES:   IT'S NOT MY
9      POSITION TO  MAKE RECOMMENDATIONS,   I DO THE WORK AND
10      I SEND THE REPORTS IN,
n                                 MR, BRAIN:  DEVIN BRAIN OF
12      THE  PROCTER  AND  GAMBLE COMPANY,   I HAD A QUESTION ON
13      YOUR GRAPHS, J.OHN, ON  WHERE YOU HAD THE PARTITION
14      COEFFICIENTS,  WHERE  THE PARTITION COEFFICIENT WAS QUITE
15      SMALL,  I CAN UNDERSTAND HOW YOUR TECHNIQUE WORKS,
16      BUT  WHEN YOU GOT DOWN  TOWARDS  THE BOTTOM, YOU'VE GOT
17      VIRTUALLY  A  HORIZONTAL LINE, NOW WHERE YOU,,,
,8                                 MR,  RHOADES: YES, WELL, NOW,
19      HERE, YOU SEE, I'VE GONE DOWN TO  A PARTITIONING
20      COEFFICIENT  THAT SAYS  1 TO 1,   IN OTHER WORDS,  IT
21      EQUALLY  DISTRIBUTES,  THE POINT HERE IS THAT IF YOU
22      EXTRACT  WITH 1 MILLILITER, YOU NOW HAVE 1 PERCENT OF
23       IT  OUT,   IF  YOU EXTRACT WITH 5 MILLILITERS, YOU  NOW
24      HAVE 5 PERCENT OF IT OUT, BUT CONCENTRATION-WISE
25       YOU'VE GAINED ESSENTIALLY NOTHING,   So YOU'RE CREEPING UP
                                  42

-------
1      ON THE TOTAL AMOUNT EXTRACTEDJ THE CONCENTRATION  IS
2      GOING DOWN VERY SLOWLY,   THIS IS THE CLUE; IF YOU
3      DO A TWO-VOLUME EXTRACTION LIKE THIS 1 AND 5 AND  THE
4      PEAK HEIGHT IS THE SAME  IN BOTH CASES, YOU KNOW,
5      YOU'RE GETTING VERY LITTLE OF IT,  IF YOU'RE GETTING
6      GOOD EXTRACTION,  THE SECOND EXTRACTION WOULD BE
7      MUCH LESS,  FOR EXAMPLE,  LET'S ASSUME YOU EXTRACT
8      100 PERCENT OF THE SAMPLE IN THE 1 MILLILITER; WHEN
9      YOU EXTRACT WITH 5 MILLILITERS, YOU SHOULD HAVE
10      20 PERCENT OF THAT.
11                                MR, BRAIN:  THE CONCENTRATION
12      WILL BE 20 PERCENT?
13                                MR, RHOADES:  THE CONCENTRATION
14      WILL BE 20 PERCENT, YES,  THANK YOU; THE TOTAL AMOUNTS,  THE
15      SAME.                      MR, BRAIN:  WHAT ARE YOU
16      SUGGESTING IN THAT CASE  WHERE YOU HAVE A FAIRLY HIGH
17      PARTITION COEFFICIENT?
18                                MR, RHOADES:  USE A SMALL
19      VOLUME IF THAT'S WHAT YOU'RE AFTER,  IN MOST OF THE
20      WORK THAT WE'VE DONE SO  FAR ON THE PRIORITY POLLUTANTS,
21      MOST OF THEM EXTRACT QUITE WELL,  So ON THAT BASIS
22      THIS TENDS TO SHOW CONCENTRATION AS YOU EXTRACT,   IT
23      SAYS IF YOU EXTRACT,,,IF YOU HAVE A MATERIAL THAT
24      EXTRACTS WELL, LIKE A HERE (INDICATING),  IF YOU KEEP
25      THE VOLUME LOW, YOU WILL  GET PREFERENTIALLY A BETTER
                                 43

-------
1       RESPONSE FOR THAT COMPOUND THAN YOU WILL  SOME  OTHERS
2      WHICH ARE NOT AS EFFECTIVELY EXTRACTED,  As  A  MATTER  OF
3      FACT, IF YOU GO UNTIL YOU GET EVERYTHING  OUT  IN  ALL
4      CASES, THEN EVERYTHING IS EXACTLY THE SAME,  DOES THAT
5      ANSWER YOUR QUESTION?
6                                MR, BRAIN:  THANK YOU,
7                                FIR, TELLIARD:   BILL,  I HAVE
8      A QUESTION,  ON THE EFFLUENTS AND THE DATA  YOU  SHOWED
9      US ON THE PHTHALATES AND SO  FORTH, WHAT WAS THE
10      AVERAGE RANGE OF SOLIDS ON THOSE SAMPLES, 20 TO  30,
11      60-80?  DO YOU HAVE ANY IDEA WHAT THE SUSPENDED  SOLIDS
12      WERE?
13                                MR, COWEN:  No, WE DON'T
14      HAVE ANY DATA ON THAT,  NONE OF THOSE MEASUREMENTS
15      WERE MADE DURING VERIFICATION,  THERE WERE  SOME
16      SAMPLES, IN ANSWER TO THE OTHER QUESTION ON  SOLIDS,
17      THERE WERE SOME SAMPLES THAT ACTUALLY HAD
18      SUSPENDED LATEX IN THEM,  UNFORTUNATELY,  WE DON'T  HAVE
19      A LOT OF DATA ON THAT RIGHT  NOW AND THAT'S  WHY
20      JOHN IS SAYING THAT WE DON'T REALLY WANT  TO SAY
21      ANYTHING ABOUT ANY OF THOSE  KINDS OF SAMPLES.
22                                MR,  WAY:   JOHN  WAY,
23      DuPoNT COMPANY,  THE QUESTION  I HAD, NOW,  I CAN.
24      UNDERSTAND HOW THIS WORKS, BUT YOU'VE SAID  NOTHING
25      ABOUT WHAT YOU USE AS THE INTERNAL STANDARDS  FOR
                                  44

-------
  1      THESE VARIOUS CLASSES  OF  COMPOUNDS, AND IT SEEMS TO ME
  2      THAT THAT'S ONE OF THE CRITICAL THINGS THAT MAKES THE
  3      WHOLE THING WORK,
  4                                 MR, RHOADES:  YES,  THAT WAS
  5      MY ASSUMPTION WHEN WE  STARTED.  So  IN  GENERAL WE TRIED
  6      TO PICK COMPOUNDS THAT WERE  SIMILAR,   WE  USED XYLENE
  7      IN SOME INSTANCES FOR  THE BENZENE,  TOLUENE,  ETHYL
  8      BENZENE,  NOW, YOU'LL  NOTICE  IN  ONE OF THOSE,  THE
  9      ETHYL BENZENE DATA WAS  NOT VERY  GOOD;  WE  HAD AN
 10      INTERFERENCE THERE WITH ONE  OF  THE  XYLENES, THE COLUMN
 11      WE HAD,   IT HAD NOTHING TO DO,  REALLY,  WITH  THE
 12      EXTRACTION,  IN THE PHTHALATES,  SOMETIMES WHAT WE DO
 13      ON THESE.,.REMEMBER, YOU  CAN  RUN THESE FAIRLY FAST,
 14      WE WOULD  TAKE A LOOK AT IT,  FOR  INSTANCE,  ON THE
 15      DIETHYL.  LET ME PREFACE  THIS BY SAYING THIS,  WE LOOKED
 16      FOR THOSE COMPOUNDS WE WERE  TOLD TO LOOK  FOR, NO MOREj
 17      SO FREQUENTLY WE WOULD JUST  MAKE A  QUICK  EXTRACTION  AND
 1«      SHOOT IT,  IF THERE WAS NO DIOCTYLPHTHALATE,  WE'D
 19      PUT IT IN, THAT WAS IT,
 20          NOW /  THE OTHER THING  THAT WE FOUND OUT IN A HURRY
 21      ON THIS, THOUGH, IS  THAT REALLY THE  ONLY THING THAT
 22      SHOULD END UP BEING DIFFERENT IS THAT  WHICH  YOU PUT
 23      IN THERE.  SO ANYTHING, ALMOST,  THAT'S THERE ACTS
 24      AS AN INTERNAL STANDARD OR REFERENCE  MATERIAL,   So
25      IN MY OPINION IT IS NOT AS CRITICAL AS I  THOUGHT IT
                                   45

-------
1      WAS INITIALLY  BECAUSE  THE ONLY REASON FOR THIS IS
2      NOT TO MAKE THE  CALIBRATION CURVE OF THE COMPOUND
3      OF INTEREST, MERELY  TO NORMALIZE YOUR DATA,
4                                 MR,  HENDERSON:  JIM HENDERSON
5      WITH CARBORUNDUM,  JOHN,  COULD WE LOOK AT THE BAR
6      GRAPH AGAINj I HAVE  A  QUESTION ABOUT THAT,
?                                 MR,  RHOADES:   THIS is A
8      THEORETICAL CALCULATION,  YOU UNDERSTAND,
9                                 MR,  HENDERSON:  Do WE NOT
10      HAVE TO MULTIPLY BY  THE VOLUME TO GET THE TOTAL
11      RECOVERY ON THESE?   IN OTHER WORDS,  THAT MIDDLE PLOT
12      SHOULD BE MULTIPLIED BY FIVE,  SHOULD IT NOT?
13                                 MR,  RHOADES:   YES,  THIS
14      SHOWS CONCENTRATION,   WHAT I WAS TRYING TO SHOW HERE
  i
15      IS THE SELECTIVITY,   IF YOU CONCENTRATED THIS 5
16      MILLILITERS TO 1 MILLILITER,,,
17                                 MR,  HENDERSON:  AND LOST
18      NOTHING,
19                                 MR,  RHOADES:  ,,.EVERYTHING
20      WOULD B.E BACK  UP HERE  (INDICATING),
21                                 MR,  HENDERSON:  WELL, IT
22      WOULD BE EXACTLY 100 PERCENT, THOUGH,
23                                 MR, RHOADES:  YES, IF YOU KEEP
24      GOING OUT,  IF YOU GO ON  OUT TO 50 MILLILITERS AND NOW, THEN, YOU MAY
25      HAVE ,100 PERCENT OF THIS ONE,  THIS IS ONE OF THE POINTS
                                  46

-------
 1      THAT  I'M TRYING TO MAKE,   IF THIS  IS THE  ONE  YOU'RE
 2      INTERESTED  IN, FINE,   IF  IT  ISN'T, DON'T  BE BURIED IN
 3      IT,
 *                                 MR, HENDERSON:   I WAS  JUST
 5      TRYING TO RATIONALIZE  THAT WITH YOUR PREVIOUS GRAPH,
 6      IT  LOOKS LIKE, IF YOU  LOOK AT THE  TOP  OF  IT,,,
 7                                 MR, RHOADES:   IF YOU'LL
 8      NOTICE HERE, THE SOLID LINE  IS THE TOTAL  PERCENT
 9      RECOVERY,   FOR INSTANCE,  JUST TAKE THE TOP ONE,   IT
10      SAYS  THAT YOU HAVE, IN  THE 1  MILLILITER YOU WOULD
11      HAVE  91 PERCENT AND, WELL, COME OUT HERE  TO 7
12      MILLILITERS, THE BEST  I CAN  TELL YOU,  YOU WOULD  HAVE
13      ABOUT 99 PERCENT OR  SOMETHING LIKE THAT,  THE CURVE
14      LINE  SHOWS  THE CONCENTRATION; THIS  I HAD  THOUGHT
15      MERELY SHOWED THAT A LITTLE  BETTER,
16                                 MR, STANKO:   GEORGE STANKO
17      FROM  SHELL  DEVELOPMENT,   I DON'T THINK THE ANSWER TO
18      MY  QUESTION IS GOING TO BE READILY AVAILABLE, BUT
19      I'M GOING TO ASK  IT  ANYWAY,   IT APPEARS THAT  WE'VE
20      BEEN  SHOWN  A METHOD  WHERE THE CONCENTRATION  FACTOR
21      is  20 TO 1.  THE STANDARD DEVIATIONS THAT WE'VE  BEEN
22      SHOWN ARE SOMEWHERE, A  THIRD  TO 20  PERCENT LESS THAN
23      WHAT  WE'VE  BEEN EXPERIENCING WITH  THE  PROTOCOL
24      PROCEDURE,AND ALSO  THE CONCENTRATION  LEVELS  THAT
25      HAVE  BEEN DISCUSSED  ARE IN THE TEN PARTS  PER  BILLION
                                   47

-------
1
       CONCENTRATION  RANGE.  Il'S A  LITTLE  DIFFICULT  FOR
2      ME TO UNDERSTAND;THE  PROTOCOL  PROCEDURE  USES  A
3      CONCENTRATION  FACTOR  OF  1,900  TO  Ij  WHEN YOU7RE
4      WORKING  IN THE TEN  PARTS  PER BILLION RANGE, OUR
5      STANDARD DEVIATIONS ARE  THREE  TO  FOUR TIMES THAT
6      OF THE METHOD  I'VE  SEEN  HERE.   SOMETHING JUST
7      DOESN'T  ADD  UP,
8                                 MR,  RHOADES:   I'M NOT
9      SURE WHETHER I COMPLETELY UNDERSTAND YOUR QUESTION,
10      LET ME SAY THIS, THAT SOME OF  THE STANDARD
11      PROCEDURES YOU REALLY, YOU CONCENTRATE FROM,,,YOU
12      EXTRACT  FROM 1,000  MILLILITERS AND YOU END UP IN
13      10 MILLILITERS,
14                                 MR,  STANKO:  THAT'S
15      1,000 TO 1.
16                                 MR,  RHOADES:  WE EXTRACT
17      FROM 100 AND END UP IN 1, WHICH IS 100 TO 1,
18                                 MR,  STANKO:  SOME OF  THE
19      DATA WERE SHOWN ON  20 TO 1 WHICH  SEEMED  TO BE THE
20      OPTIMUM,
21                                 MR.  PROWS:  Mo,  WELL,
22      YOU DO NOT EXTRACT  ALL COMPOUNDS  WITH THE SAME
23      EFFICIENCY AT  ALL LEVELS,  WHAT I THINK THAT  WE'RE
24      TRYING TO SAY  HERE  IS THAT THE RECOVERIES ARE GOOD
25      EVEN DOWN TO 100 AND  LESS; I WOULD THINK.  I'VE DONE
                                  48

-------
1       SOME OF THIS WITH A GALLON WITH A MILLILITER,  JUST
2      TO SEE IF SOMETHING'S THERE AND YOU CAN DO  THIS,-
3      YOUR QUANTITATION BEGINS TO FALL APART, HOWEVER,
4                                MR, STANKO:  WELL, THE
5      BOTTOM LINE.  IT APPEARS THAT YOU HAVE A TREMENDOUS
6      INCREASE IN PRECISION OF ANY METHODS THAT WE'VE
7      SEEN AND SOMEWHERE BETWEEN A 10 AND A 50-FOLD
8      INCREASE IN SENSITIVITY, WHICH IS HARD TO EXPLAIN,
9                                MR, RUSHNECK:  GEORGE,
10      LET ME ATTEMPT TO EXPLAIN THAT,   DALE RUSHNECK,
11      PJB LABS,  IT'S REALLY DEPENDENT ON THE COMPOUND,
12      A LOT OF THESE MICROEXTRACTION PROCEDURES USE  THE
13       ELECTRON  CAPTURE DETECTOR FOR WHICH YOU DON'T
14      NEED AS GREAT A CONCENTRATION FACTOR,  THAT APPLIES
15      TO THE PHTHALATES, GENERALLY TO THE CHLORINATED
16      VOAS, TO THE PESTICIDES, AND SOME OF THE OTHER THINGS,
17      YOU NEED THE CONCENTRATION FACTOR, FOR EXAMPLE,
18      WHEN YOU'RE USING A FLAME IONIZATION DETECTOR  BECAUSE
19      THE SENSITIVITY ISN'T AS GREAT, AND THEREFORE,
20      ALTHOUGH WE NORMALLY USE MICROEXTRACTION AT 100 TO
21      1, WHEN WE HAVE, LI KE, THE PHENOLS AND WE NEED TO
22      DETECT THEM DOWN AROUND 10 MICROGRAMS PER LITER/WE
23      HAVE TO GO TO THE BIG EXTRACTION,  THE EXTENSIVE
24      EXTRACTION, IN ORDER TO GET THAT DETECTION  LEVEL,
25                                MR, STANKO:  WELL, I  THOUGHT
                                  49

-------
1      THE DATA THAT WAS SHOWN HERE WAS  ON  PHENOLS  AND  I
2      DON'T BELIEVE THAT APPLIES,
3                                MR,  RUSHNECK:   YES, BUT  I
4      DON'T BELIEVE THOSE LEVELS WERE DOWN AROUND  10
5      MICROGRAMS PER LITER, WERE THEY?
6                                MR,  COWEN:   WELL,  THE  LEVELS
7      VARY; WE COULDN'T PUT ON EACH  ONE, YOU KNOW,  YOU'D HAVE
8      TO PUT  EACH  NUMBER WITH  ITS  LEVEL.   THEY  ARE ALL
9      ABOVE 10, BUT THAT  IS ALL  I  CAN  SAY, THEY ARE ALL
10      OVER THE PLACE,  THEY ARE ALL SORTS OF  SAMPLE TYPES,
11                                MR,  STANKO:   THE STANDARD
12      DEVIATION FOR ANALYSES WILL  BE MUCH  DIFFERENT IF YOU'RE
13      ANALYZING AT 1,000 PARTS PER BILLION VERSUS  100  PARTS
14      PER BILLION  OR 10 PARTS PER  BILLION;  YOUR DATA
15      REALLY  NEEDS TO  BE QUALIFIED THERE.
16                                FIR.  COWEN:   WELL,  WE SHOULD
17      BREAK IT UP  INTO CONCENTRATION RANGES,  THAT'S TRUE,
18      FOR NOW WE WERE  TRYING TO SEE  WHAT IT  IS  WITHOUT REGARD
19      TO CONCENTRATION.
20                                MR.  STANKO:   THANK YOU,  SIR,
21                                MR,  TELLIARD:   BEFORE  ANYONE
22      ELSE CAN GET TO  A MICROPHONE,  THANK YOU VERY  MUCH
23      KATHY,  GEORGE, BILL,  WE'RE  GOING TO TAKE A  BREAK  NOW
24      AND YOU'VE GOT TEN MINUTES TO  GET YOUR COFFEE AND  EAT
25      YOUR PEAR AND GET BACK  IN HERE,
                                  50

-------
 i                                 MR,  TELLIARD:   LAST YEAR,
 2       THE  LAST  MEETING  WE  HAD, BRUCE  COLBY FROM SYSTEMS/
 3       SCIENCE AND  SOFTWARE GAVE A PRESENTATION ON,
 4       FOR  LACK  OF  A  BETTER TERM,  ISOTOPE  DILUTION OR THE STABLE
 5       LABEL  APPROACH IN VOASj  SINCE  THEN  BRUCE HAS BEEN
 6       LOOKING AT THE APPLICATION TO  A MUCH LARGER RANGE
 7       OF SAMPLES AND I  THINK MOST OF THE  BRANCH CHIEFS IN
 8       EGD  WHO ARE  PAYING ALL THIS MONEY FOR ANALYSIS ARE
 9       KIND OF HOPING THAT  WE MIGHT FIND A METHOD HERE TO
10       SAVE ME A FEW  DOLLARS,   NOW,  I KNOW FOR  ALL YOU
11       CONTRACTORS  THAT  MAKES YOU FEEL WARM AND FUZZY
12       INSIDE, THE  THOUGHT  OF ME SAVING A  FEW DOLLARS,  BUT
13       ALSO I THINK IT MIGHT BE AN ALTERNATE SOLUTION TO
14       THE  27 SPIKES,  15 ALIQUOTS, 37 RECOVERIES AND CUT
15       DOWN A LITTLE  BIT ON THE REPETITION THAT WE'RE
16       PRESENTLY RUNNING; 33 RUNS TO  GET 12 DATA POINTS IS
17       SOMEWHAT  EXPENSIVE,AND IN THE  BACK  OF OUR MINDS
18       THESE  ARE SOME OF THE SECRET THOUGHTS, WE'RE HOPING
19       AGAIN  THAT WE  WILL MICROEXTRACT IT  AND STABLE IT
20       AND  RUN IT AND I  CAN GO HOME AND SIT AROUND THE HOUSE
21       AND  WATCH ALL  THE DATA ROLL IN,
22           BRUCE HAS  BEEN AT IT UNDER A CONTRACT THROUGH
23       RTF  AND LARRY  JOHNSON'S FOLKS  HAVE  SPONSORED THE
24       CONTRACT  AND BRUCE IS HERE TODAY TO GIVE US KIND OF
25       AN UPDATE ON HOW  FAR HE IS WITH WHAT HE'S LOOKED AT,
                                 .51

-------
i       EVALUATION OF STABLE LABELED COMPOUNDS AS INTERNAL

2         STANDARDS FOR QUANTITATIVE GC/MS ANALYSIS

3                   BY:  DR,  BRUCE E,  COLBY

4
        I  THINK FIRST OF ALL I'D LIKE TO SAY WHAT WE RE
5
     DOING, IN LOOKING AT THE USE OF STABLE LABEL
6
     COMPOUNDS AS INTERNAL STANDARDS ON A *ER COMPOUND

     BASIS, IS NOTHING NEW; IT'S BEEN GOING ON FOR ABOUT
Q
     THE LAST L\Q OR SO YEARS, AND  IT'S A SITUATION THAT
9
     HAS BEEN APPLIED  ALMOST EXCLUSIVELY IN BIOLOGICAL
10
     MEDIA WHERE PEOPLE WERE INTERESTED  IN A SPECIFIC

     COMPOUND AS OPPOSED TO BEING  INTERESTED IN A  LARGE

     RANGE OF COMPOUNDS.   As A  CONSEQUENCE,  THE METHODOLOGY
13                                                  T  /
     HAS DEVELOPED  ALONG FAIRLY EMPIRICAL  LINES,   IT S
14
     FAIRLY STRAIGHTFORWARD TO  GO  IN AND TRY  IT THIS WAY,

     TRY  IT THAT WAY,  MAKE SOME DECISIONS  ON WHAT  THE  BEST
16
     WAY TO DO  IT  FOR  THIS COMPOUND IS,  AND  THEN PROCEED ON
17                                      .,
     FROM  THERE  TO  APPLY THE METHOD,   WHEN WE  GET

      INTO  LOOKING  AT  SOME  40 OR 50 COMPOUNDS IN A  GIVEN  RUN,
19
      IT'S  NOT AS EASY  TO DO IT  FROM AN EMPIRICAL
20
      STANDPOINT,1 RATHER WE HAVE TO HAVE SOME SORT  OF

      LOGICAL,  REASONABLE,  TIME-EFFICIENT WAY TO GO AT

      PICKING  THE IVE'S THAT SHOULD GIVE US THE BEST

      OR AT LEAST VERY GOOD RESULTS IN TERMS OF THE
24
25     ANALYTICAL WORK,   WHAT WE'RE REALLY DOING IS TO SPIKE
                                52

-------
 1

      EVERY GIVEN COMPOUND INTO EVERY SAMPLE, ONLY IN
 2


 3     SPIKING IT INTO THE SAMPLE, WE PERTURB THE COMPOUND



 4     OR CHANGE THE COMPOUND BY LABELING IT, STABLE


 5     ISOTOPICALLY LABELING IT, AND IN THIS WAY THE MASS


 6     SPECTROMETER CAN TELL US THAT THIS ENTITY WAS WHAT


 7     WE SPIKED IN, THIS OTHER ENTITY, THE SAME COMPOUND,


 8     BUT DIFFERENT, NATURALLY ABUNDANT LABELING IS


 9     WHAT WAS THERE TO BEGIN WITH.  So IF WE WANT TO


10     MEASURE PHENOL, WE'LL SPIKE A LABELED PHENOL


11     AND DETERMINE RECOVERY FROM THE LABELED PHENOL


12     IN THE SAME RUN EXACTLY AS WE'RE MAKING OUR MEASURE-


13     MENT,  THIS WAY WE CANCEL OUT, AS WAS MENTIONED


14     EARLIER, A LOT OF THE VARIABLES THAT CAN EXIST IN


15     ANALYZING MULTIPLE SAMPLES,  IT ALSO COSTS LESS


16     MONEY BECAUSE WE ONLY HAVE TO DO IT ONE TIME,  THERE


17     IS ONE PREPARATION AND ONE ANALYSIS; THERE'S A


18     LITTLE MORE DATA, BUT NOT ANY MORE DATA THAN ONE


      WOULD ENCOUNTER IN SPIKING A SAMPLE IN ADDITION

20
      TO THE ORIGINAL SAMPLE,


        THE FIRST SLIDE, IF I CAN HAVE IT, WILL JUST

22
      GIVE US A QUICK LOOK AT WHAT WE'RE LOOKING FOR IN

23
      TERMS OF THE EVALUATION OR ACQUISITION OF RECOVERY


      INFORMATION,  IDEALLY, WE'D LIKE TO GET RECOVERY
25
      INFORMATION ON EVERY COMPOUND THAT IS ON THE
                                 53

-------
                                     RECOVERY  INFORMATION
            SITUATION
                    INFORMATION
                                         METHOD
           IDEAL
Ul
UJ
ACCEPTABLE
           POTENTIAL
           ALTERNATIVE
EVERY COMPOUND IN
EVERY SAMPLE

MOST COMPOUNDS IN
EVERY TENTH SAMPLE
OF EACH MATRIX

MOST COMPOUNDS IN
EVERY SAMPLE
SPLIT SAMPLE, SPIKE ONE PORTION,
ANALYZE BOTH PORTIONS

SPLIT ONE OUT OF EVERY TEN SAMPLES
FROM A GIVEN MATRIX, SPIKE ONE
PORTION, ANALYZE BOTH PORTIONS

SPIKE EACH SAMPLE WITH STABLE
ISOTOPICALLY LABELED ANALOGS OF
MOST COMPOUNDS

-------
 1        PRIORITY  POLLUTANT  LIST,   THE WAY ONE WOULD DO
 2        THAT,  OF  COURSE,  IS TO  SPIKE  EVERY SAMPLE AFTER
 3        IT  HAS BEEN  SPLIT AND TO  ANALYZE BOTH PORTIONS,
 4        THE REASON  I  THINK  SPIKING EVERY COMPOUND IS
 5        IMPORTANT IS  THAT IF WE,  IN FACT,  DO NOT RECOVER
 6        ANY TCP.,  SAY,  WE  DON'T  KNOW FOR  SURE WHETHER THAT'S
 7        BECAUSE THERE IS  NO TCP. PRESENT,  OR WHETHER IT'S
 8        REALLY PRESENT BUT  WE'RE  JUST NOT RECOVERING ANY
 9        OF  IT,  IF WE SPIKED TCP  INTO THE SAMPLE AND
 10        COULDN'T  RECOVER  THAT,  WE'D KNOW THAT THERE WAS
 11        SOMETHING TO  BE CONCERNED ABOUT,   IF WE  SPIKE IT
 12        AND DO RECOVER IT,  THEN WE KNOW  AT LEAST THAT OUR
 13        ANALYTICAL METHOD IS FUNCTIONING,
 14            THE  AMOUNT OF  EFFORT THAT WOULD GO  INTO
 15        THAT KIND OF  A SPIKING  SITUATION  GETS TO BE
 16        PRETTY LARGE  AND  IT CAN GET EXPENSIVE AND TIME-
 17        CONSUMING AND SO  ON, SO THE IDEA HAS BEEN THAT
 is        WE'LL  SPIKE LESS  THAN ALL THE SAMPLES, SAY ABOUT
 19        10  PERCENT OF THEM,  ON  AN OVERALL BASIS  AND DO
 20        OUR  RECOVERIES ON THOSE 10 PERCENT AND INFER ON
 21        THE  OTHER 90  PERCENT THAT THAT'S  VALID INFORMATION,
 22            IN PRACTICE, IT SEEMS TO BE  TURNING OUT
 23        THAT ABOUT 50 PERCENT OF  THE  SAMPLES ACTUALLY
 24        END  UP  BEING  SPIKEB WITH  THE  QA  THAT'S BEING
25

-------
1       APPLIED NOW ON A PER-EVENT BASIS,  THE 10 PERCENT
2      NUMBER IS MORE ASSOCIATED WITH, SAY, 1,000 SAMPLES
3      FROM ONE PARTICULAR OUTFALL BEING LOOKED ALAND THAT
4      IS NOT THE WAY THESE THINGS ARE BEING DONE; THE
5      10 PERCENT WOULD BE BASED ON, SAY, FIVE YEARS FROM
6      NOW SOMEBODY'S BEEN MONITORING THEIR EFFLUENT  FOR
7      THAT PERIOD OF TIME, IT PROBABLY WOULD DROP DOWN
8      TO ABOUT 10 PERCENT,  WHAT I AM SUGGESTING, THE
9      POTENTIAL ALTERNATIVE WOULD BE TO SPIKE, AND  I'M
10      SAYING MOST OF THE COMPOUNDS, I THINK THAT THERE ARE
11      SOME THAT THERE'S NOT TOO MUCH REASON TO SPIKE;
12      THERE'S NO REASON, FOR EXAMPLE, TO PUT TCDD INTO
13      THE WORLD IF WE DON'T NEED TO, AND TO LOOK AT  THE
14      SPIKED SAMPLE WHICH IS THE ONLY SAMPLE,  WE NOW
15      ARE BACK TO A VERY LOW LEVEL OF INCREASED ANALYTICAL
i6      WORK, WE HAVEN'T  INCREASED THE NUMBER OF SAMPLES
17      THAT WE NEED TO RUN AND WE STILL GET ALL OF THE
18      INFORMATION THAT WE WOULD LIKE TO GET IN THE  IDEAL
19      SITUATION; THAT'S AT LEAST THE HYPOTHESIS,
20          THE PROBLEMS THAT MIGHT BE ASSOCIATED WITH
21      DOING THIS, OR AT LEAST SOME OF THE MORE  IMPORTANT
22      ONES, ARE LISTED IN THE NEXT SLIDE,  THE QUESTION
23      OF COST AND AVAILABILITY OF ALL OF THESE COMPOUNDS,
24      I GUESS I ALLUDED TO IT LAST YEAR AND IT SEEMED
25      LIKE IT WOULD BE FAIRLY FAVORABLE, BUT NOT GREAT,-
                                   55

-------
   FEASIBILITY QUESTIONS OF STABLE ISOTOPE METHOD






1,  COST/AVAILABILITY OF NECESSARY LABELED COMPOUNDS?



2,  WILL LABELS EXCHANGE WITH SAMPLE MATRIX?



3,  WHAT ARE THE EFFECTS OF ISOTOPIC PURITY?



1,  HOW SHOULD THE DATA BE HANDLED?




5,  WHAT ABOUT INSTRUMENT VARIABLES?

-------
i            THAT SITUATION SEEMS TO BE CHANGING VERY
2       RAPIDLY, AND I EXPECT THAT A VERY LARGE PERCENTAGE
3       OF THESE COMPOUNDS WILL BECOME AVAILABLE IN THE
4       NEXT YEAR,  THE QUESTION OF EXCHANGE OF LABELS
5       WITH THE SAMPLE MATRIX IS A CONCERN,  WHAT
6       HAPPENS IF WE PUT OUR LABELED COMPOUND IN AND
7       THE LABEL COMES OFF OF THAT COMPOUND?  WELL,
8       CLEARLY THAT WOULD AFFECT THE RELIABILITY OF THE
9       ANALYSIS, AND SO SOMETHING HAS TO BE DONE TO
10       EVALUATE THAT SITUATION, AND I'LL EXPLAIN A LITTLE
11       EXPERIMENT THAT WE DID TO AT LEAST GET A START ON
12       THAT,  WE DON'T KNOW ESSENTIALLY WHAT THE EFFECTS
13       OF ISOTOPIC PURITY ARE, OR DO WE?  WELL, WE'LL
14       GET  INTO SOME MATHEMATICS IN A MINUTE THAT WILL
15       DEMONSTRATE THAT THIS SHOULDN'T BE A CONCERN FOR
16       THE ANALYSIS,  THE PAST DOES NOT EXPLAIN TO US
17       PRECISELY HOW WE SHOULD HANDLE THE DATA, AND I
18       BELIEVE WE NOW KNOW HOW TO DO THAT VERY RELIABLY,
19       so WE'LL TOUCH UPON THAT SOME,
20            INSTRUMENT VARIABLES; WE'VE LOOKED AT THAT,
21       ALL  I CAN SAY IS THAT I HAVEN'T BEEN ABLE TO TUNE
22       AN INSTRUMENT (SORRY IF I'M NOT SUPPOSED TO TALK ABOUT
23       TUNING), SUCH THAT WE CAN SERIOUSLY AFFECT AN  ISOTOPE
24       RATIO,  THE TUNING OF THE INSTRUMENT AFFECTS ABUNDANCE
25
                                  .56.

-------
 1       PATTERNS SEVERELY, BUT BECAUSE THE MEASUREMENTS



 2       THAT WE MAKE IN DOING THE ISOTOPE RATIOIN^ ARE




 3       VERY CLOSE TOGETHER ON THE MASS SCALE, THERE  IS




 4       VERY LITTLE DISTORTION OF THE ISOTOPE RATIO,  AND




 5       IT'S SO VERY SMALL, AT LEAST AS FAR AS WE NEED TO




 6       CONTEND WITH IT, THAT IT'S IGNORABLE,



 7            THE COST,  IF  I CAN GO BACK TO THAT, AND  THE



 8       AVAILABILITY OF COMPOUNDS IS SHOWN IN THE NEXT




 9       SLIDE BY FRACTION,  THERE ON THE TOP LINE ARE THE



10       AVAILABLE COMPOUNDS IN TERMS OF WHAT 13 CURRENTLY



11       IN THE CATALOGS THAT THE LABELED COMPOUND MANU~




12       FACTURERS HAVE,  PHENOL D6, WHICH IS VERY EASILY



13       CHANGED TO D5,  IS THE ONLY ACID COMPOUND THAT'S




14       THERE; THERE WERE 13 BASE/NEUTRALS AND 15 OF  THE




15       VOLATILE COMPOUNDS,  THE MANUFACTURERS HAVE



16       AGREED THAT THEY INDEED CAN SYNTHESIZE ANYTHING



17       YOU WANT, AND  IN FACT, WE'VE GOT QUOTES NOW ON




18       A VERY LARGE PERCENTAGE OF THESE COMPOUNDS, AND




19       IT SEEMS THAT  WE'LL BE PURSUING THAT, SO THE  LIST



20       WILL CHANGE VERY RAPIDLY NOW,




21            IF WE LOOK AT A COST ASSOCIATED WITH THE



22       COMPOUNDS NOW, AND ASSUMING THAT WE'RE GOING  TO SPIKE




23       ALL PRIORITY POLLUTANTS, THE DOLLARS PER SAMPLE ARE



24       GIVEN ON THE BOTTOM (INDICATING), AND THEY LOOK



25
                                 57

-------
                                           COST/AVAILABILITY
                            ACID COMPOUNDS
                                   BASE/NEUTRAL COMPOUNDS
                                        VOLATILE COMPOUNDS
             CATALOG
              ITEMS
             (NUMBER)
                                             13
                                                15
Ln
-J
  CUSTOM
SYNTHESIS
 (NUMBER)
10
  16
               COST
             ESTIMATE
          PER SAMPLE ($)
                    1,15
                     4,00
,003
                  ESTIMATED COST PER SAMPLE ANALYSIS = $5,15

-------
 1       LIKE VERY SMALL NUMBERS, AND  INDEED  THEY  ARE,
 2       BECAUSE WE DON'T HAVE TO SPIKE THE SAMPLE WITH
 3       VERY MUCH OF THE COMPOUND,  THE  COSTS  IN  PURCHASING
 4       THE COMPOUND ARE BASED ON  PURCHASING A GRAM,  SO
 5       IF SOMEONE SOMEWHERE BUYS  A GRAM, HE COULD THEN
 6       METER THIS OUT AS NEEDED TO PEOPLE DOING  THE
 7       ANALYSES, AND ON A PER-ANALYSIS  BASIS,  THE COST
 8       BECOMES VERY LOW—A TOTAL  OF  ABOUT $5,15  FOR
 9       MATERIALS BASED ON QUOTATIONS FOR THESE COMPOUNDS,
10       THE $5,15 BECOMES REALLY INSIGNIFICANT WHEN YOU
11       THINK THAT SOMEONE'S GOT TO PACKAGE  THESE THINGS
12       UP AND DO ALL THE OTHER THINGS THAT  HAVE  TO BE
13       DONE WITH STANDARDS, KEEP  TRACK  OF THEM AND
14       PUT THEM IN LITTLE VIALS,  SEND THEM  HERE,  SEND
15       THEM THERE,  THE $5 JUST DISAPPEARS  INTO  THE
16       NOISE LEVEL OF THE COST DATA,
17            THE CUSTOM SYNTHESIS  AND CATALOG  ITEMS
18       THAT WERE INCLUDED IN THIS ESTIMATE  INCLUDED
19       PRIMARILY DEUTERATED COMPOUNDS,  BUT  THERE ARE
20       SOME DEUTERATED COMPOUNDS  THAT DO SHOW
21       EXCHANGE,  ALSO, THERE ARE SOME  COMPOUNDS THAT
22       CANNOT BE DEUTERATEDj PENTACHLOROPHENOL,
23       HEXACHLOROETHANE, HEXACHLOROBENZENE, THINGS LIKE
24       THAT, WE CAN'T DEUTERATE THOSE,  so THE  COST IN THOSE
25
                                 58

-------
 1        CASES  WAS  BASED ON  C13 LABELED COMPOUNDS,   THEY
 2        ARE MORE EXPENSIVE,  BUT CLEARLY DON'T AFFECT THE
 3        OVERALL PRICE  OF THINGS VERY MUCH,   THE CONCERN
 4        FOR EXCHANGE WITH THE  MATRIX IS ONE THAT WE'VE
 5        LOOKED AT  AS BEST WE CAN,  I  THINK,  AT THIS STAGE,
 6        AND THE WAY WE DID  THAT IS ILLUSTRATED IN THE
 7        NEXT SLIDE.
 8            WE FELT THAT WHAT WE'RE TRYING TO LOOK FOR
 9        IS, SAY, WITH  CHLOROFORM HERE,  THE  EXCHANGE OF
10        THE DEUTERIUM,  IF WE WERE  GOING TO  USE DEUTERATED
11        CHLOROFORM, WITH A  PROTON  FROM SOLUTION,   I DON'T
12        MEAN TO IMPLY  THAT  THIS EXCHANGE TAKES PLACE
13        IN AN  ACIDIC SOLUTION  OR ANYTHING ELSE;  JUST THAT
14        THERE'S A  PROTON OUT HERE  SOMEWHERE AND IT CAN
15        EXCHANGE,  AND  NOW WE HAVE  CONVERTED OUR INTERNAL
16        STANDARD TO THE PRIORITY POLLUTANT, AND THAT
17        WOULD  INCREASE THE  APPARENT  CONCENTRATION OF
18        CHLOROFORM IN  THE SAMPLE,
19            THE WAY TO STUDY  THIS IS NOT NECESSARILY
20        TO GO  OUT  AND  BUY DEUTERATED CHLOROFORM,
21        BECAUSE IF WE  GOT INOT BUYING ALL OF THE  DEUTERATED
22        COMPOUNDS,  IT  WOULD  GET VERY EXPENSIVE,  AND WE
23        WOULD  UNNECESSARILY  PURCHASE SOME THAT WOULDN'T
24        WORK,  SO  WHAT WE DO IS LOOK AT THE NATURALLY
25        ABUNDANT MATERIAL,  REGULAR CHLOROFORM, BUT WE'LL
                                  59

-------
                                   ISOTOPE  EXCHANGE STUDY
                            EXCHANGE IN  AN ANALYTICAL SITUATION:
                                               cna
Ul
EXCHANGE STUDY:
      CHCI3  + D+^-CDa3 + H+

CONDITIONS STUDIED:
      pD       = 2, 7, 12
      TIME  (HR) = 0, 18, 96
      TEMP  (QC) = 0, 25

-------
1        PREPARE IT IN A DEUTERATED ENVIRONMENT AND WE'LL
2       STORE IT FOR A WHILE AND WE'LL ADJUST THE Pi),
3       THE EQUIVALENT OF PH,  AND SEE WHAT HAPPENS, SEE
4       IF WE CAN FIND SOME SITES ON SOME MOLECULES THAT
5       DO EXCHANGE, AND THEN WE'LL KNOW THAT THOSE ARE
6       ONES THAT WE SHOULDN'T TRY TO LABEL.
7            WELL, HERE ARE THE CONDITIONS ON THE BOTTOM
8       (INDICATING),  HE LOOKED AT pDs OF 2, 1, AND
9       12, AND WE LOOKED AT THESE OVER TIME PERIODS
10       OF 0, WHICH  IS CLOSE TO 0, /!8 AND 96 HOURS, AND
11       WE LOOKED AT TEMPERATURES OF CLOSE TO 0 AND
12       ABOUT 25 DEGREES,  So WE'VE COVERED SITUATIONS
13       THAT WOULD BE ON THE EXTREMES OF THE REQUIREMENTS
14       FOR THE SAMPLE PREPARATION AS IT IS RIGHT NOW,
15            WHEN WE WENT THROUGH THIS EXPERIMENT  WITH
16       ALL OF THE COMPOUNDS THAT WE COULD GET  IN
17       SUFFICIENT QUANTITIES FOR STUDY, WE FOUND THAT
is       THERE WEREN'T VERY MANY THAT DID SHOW EXCHANGE.
19            THE NEXT SLIDE SHOWS WHICH ONES THOSE ARE,
20            IN THE  ACID FRACTION, ALL OF THE PHENOLIC
21       PROTONS EXCHANGE;  THERE ARE OTHER  PROTONS ON
22       THE RINGS THAT WE  COULD  LABEL, SO THE PHENOLIC
23       PROTON  PROTON  IS  NO REAL CONCERN  THERE.   IN
24
25

-------
                                  COMPOUNDS EXHIBITING EXCHANGE
                                         ACID COMPOUNDS
                                  ALL PHENOLIC PROTONS EXCHANGED
                                       VOLATILE COMPOUNDS
                                  CHLOROFORM
w                                 DlCHLOROBROMOMETHANE
o
>                                 CHLORODIBROMOMETHANE
                                  BROMOFORM
                                  TRICH.LOROETHYLENE

                                     BASE NEUTRAL  COMPOUNDS
                                  FLUORENE

-------
1       THE VOLATILE  FRACTION,  ALL THE  TRIHALOMETHANES
2      EXCHANGED;  THEY  EXCHANGE  VERY EFFECTIVELY IN A
3      BASIC  MEDIUM,  THESE WOULD HAVE TO BE LABELED
4      EITHER WITH CHLORINE 35 OR 37 OR WITH THE CARBON
5      13.   CARBON 13 CHLOROFORM is ALREADY AVAILABLE,
e      so  THAT'S  NOT A  PROBLEM,   WE FOUND ONE BASE/
7      NEUTRAL COMPOUND,  FLUORENE, WHICH EXCHANGED, AND
8      WE  BELIEVE THAT  TO BE THE TWO PROTONS WHICH ARE
9      ALIPHATIC  IN CHARACTER COMPARED TO THE REMAINING
10       PROTONS ON THAT  COMPOUND,
n            l^ELL, THE COST DOESN'T LOOK BADj SOME
12       EXCHANGE DOES TAKE PLACE, BUT WE CAN WORK AROUND
13       IT  IN ALL OF THE CASES,  THE NEXT THING BECOMES,
14       HOW DO WE REALLY GO ABOUT SETTING UP AN ANALYSIS
15       FOR MANY COMPOUNDS?  As  I MENTIONED, GOING AT
16       IT  EMPIRICALLY WOULD BE JUST ONE HECK OF A TASK,
17       AND FRANKLY,  I WOULDN'T WANT TO UNDERTAKE IT,  THE
18       WAY TO GO AT  IT, THEN, WOULD HAVE TO BE ON SOME
19       SORT OF SYSTEMATIC BASIS, AND AS A RESULT, WE FELT
20       THAT THE WAY TO DO THIS WAS TO GO BACK AND LOOK AT
21       THE MODEL  PER SE OF THE  PRINCIPLE OF  ISOTOPE DILUTION
22       AND SEE WHERE THAT WOULD TAKE US  IF WE  LOOKED AT THE
23       PARTICULAR PARAMETERS THAT  WE  HAVE TO DEAL WITH,
24       WE HAVE TO SELECT M/E's,  MASSES THAT WE'RE GOING
25       TO MAKE OUR MEASUREMENTS AT,   HELL,  THAT  SOUNDS
                                 61

-------
1      PRETTY EASY,  IT REALLY IS, BUT WHEN YOU GET  INTO
2      100 COMPOUNDS OR SOMETHING THAT GETS TO BE A  LOT OF
3      WORK IF YOU HAVE TO CHECK EACH ONE OUT SEPARATELY,
4          THE QUESTION OF, WELL, HOW MUCH DO WE SPIKE  INTO
 5      THE SAMPLE  IS ANOTHER CONCERN,  AGAIN, THAT'S
 6      SOMETHING THAT'S NOT APPROPRIATE TO DO ON AN
 7      EMPIRICAL BASIS,  HOW DO WE CALCULATE THE RESULTS?
 s      THERE ARE ANY NUMBER OF WAYS IN THE LITERATURE
 9      THAT ARE GIVEN FOR THAT SORT OF THING, AND IT  HASN'T
10      BEEN TOTALLY CLEAR WHICH ONE SHOULD BE USED AND
11      WHEN,  THE  RELATIONSHIP BETWEEN THOSE DIFFERENT
12      CALCULATING METHODS DOES NOW EXIST IN PRINT,  AND
13      AS A RESULT WE'RE ABLE TO TAKE THAT AND MAKE  SOME
14      GUESSES,
15          ANYWAY,  LET'S LOOK AT THE MODEL A LITTLE  BIT
16      BECAUSE I'M GOING TO TALK ABOUT THE MODEL, AND THE
17      NEXT SLIDE GIVES US A FAIRLY CLEAR IDEA, I THINK,
is      OF WHAT'S GOING ON WHEN WE TALK ABOUT ISOTOPE
19      DILUTION; IT DOESN'T MATTER WHAT KIND IT IS IN
20      THIS SORT OF SLIDE, WHETHER IT'S INORGANIC OR  ORGANIC
21      OR ANYTHING ELSE,  WHAT WE'RE DOING IS WE'RE  TAKING
22      THE PURE COMPOUND X, AND V.'E'LL CALL IT THE NATURALLY
23       ABUNDANT MATERIAL THAT'S IN THE SAMPLE TO BEGIN
24       WITH,  IN THE EQUATIONS, WE'RE USING THE X AS AN
25
                                62

-------
PRINCIPLE  OF  ISOTOPE  DILUTION
  PURE x
Rv=
   PURE y
   MIXTURE,
           m/e  a b
                             yb
                62A

-------
 1       INDICATION OF THE NUMBER OF MOLES OF THAT  COMPOUND
 2       PRESENT,
 3            FOR PURE X, THERE ARE TWO M/E'S WHICH  EXIST
 4       WHICH GIVE US AN ISOTOPE RATIO, RX, WHICH  IS
 5       GIVEN BY THE ABUNDANCE OF THE IONS AT M/E A OVER
 6       THE IONS AT M/E B,   $0 IT'S JUST THE AREA OF
 7       A OVER THE AREA OF B, AND THAT'S VERY EASILY
 8       DERIVED FROM THE DATA,  THERE ALSO EXISTS FOR
 9       THE LABELED COMPOUND Y THAT WE'RE GOING TO ADD
10       AN ISOTOPE RATIO, Ry, WHICH HAS ABUNDANCES AT
11       M/E'S A AND B WHICH, AGAIN, GIVES US AN ISOTOPE
12       RATIO,   THOSE SHOULD BE CONSTANT IN TIME,  VE
13       DON'T EXPECT THOSE EVER TO CHANGE UNLESS WE
14       CHANGE, SAY, THE MANUFACTURE OF Y, AT WHICH
15       POINT WE'D HAVE TO GO BACK AND REMEASURE THAT
16       VALUE,
17            ANYWAY, IF WE TAKE AN UNKNOWN QUANTITY OF
18       X AND MIX IT WITH A KNOWN QUANTITY OF Y, WE COME
19       UP WITH A MIXTURE WHICH HAS PRODUCED AN ISOTOPE
20       RATIO THAT BY DEFINITION HAS TO BE BETWEEN RX
21       AND Ry, AND IT IS DEFINED OR GIVEN.. BY THE
22       RELATIONSHIP THAT'S SHOWN,   WHEN THIS IS SOLVED
23       FOR X/Y, THE MOLE RATIO OF SAMPLE TO INTERNAL
24       STANDARD CAN BE EXPRESSED SOLELY AS ISOTOPE
        RATIOS,  THAT is, BY KNOWING THE AMOUNT OF INTERNAL
                                63

-------
1        STANDARD  ADDED,  WE CAN VERY EASILY CALCULATE THE



2       QUANTITY  OF UNLABELED COMPOUND ORIGINALLY PRESENT



3       IN THE SAMPLE,   THAT'S THE WHOLE PRINCIPLE OF



4       ISOTOPE DILUTION,



5            NOW, I'VE KIND OF SKIPPED OVER ONE LITTLE



6       THING HEREj WE DON'T KNOW MANY ORGANIC COMPOUNDS



7       THAT HAVE ONLY TWO ISOTOPE PEAKS IN THEIR MASS



8       SPECTRUM,  AS A RESULT, THERE'S ANOTHER TERM IN



9       HERE WHICH I'VE LEFT OUT BECAUSE IT DOESN'T



10       REALLY HAVE MUCH BEARING ON WHAT THE MODEL IS



11       GOING TO  TELL US,   THE OTHER ISOTOPES AND FRAGMENT



12       IONS AND EVERYTHING ELSE THAT THE SPECTRA HAVE IN



13       THEM END UP AS TERMS OVER HERE ON THE RIGHT-HAND



14       SIDE (INDICATING),  THERE WOULD BE A TERM HERE



15       WHICH WOULD CONSIST OF THE VALUE 1 MINUS THE



16       ABUNDANCE OF THE OTHER ISOTOPES AND DIVIDED BY



17       1 MINUS THE NUMBER OR QUANTITY OF OTHER  ISOTOPES



18       IN EACH CASE,  So WHAT WE HAVE, THEN, IS ANOTHER



19       TERM OUT HERE, THE INVISIBLE TERM, AND IF SOMEONE



20       WANTS TO SEE WHAT IT REALLY IS AND WHAT  IT LOOKS



21       LIKE,  I HAVE THAT IN MY NOTES AND I CAN  SHOW  IT



22       TO YOU LATER, BUT IN ESSENCE, IT ALWAYS  CANCELS



23       OUT  FOR ORGANIC MOLECULES,  FOR THE PURPOSE OF



24       USING THIS MODEL TO PREDICT,  IT'S JUST MORE



25       SIMPLE TO  LEAVE IT OUT FOR NOW, THEN SEE IF,  IN
                                64

-------
 1       FACT, THE PREDICTIONS AGREE WITH  THE  EXPERIMENTAL
 2       RESULTS,  IF THEY DO, WELL, LET'S NOT WORRY
 3       ABOUT IT,  IF THEY DON'T AGREE, LET'S TRY  TO
 4       WORK THE MODEL.  IN THE MORE COMPLICATED FORM,
 5       IT TURNS OUT THAT THE MODEL IN THE  SIMPLIFIED
 6       FORM WORKS ADMIRABLY, SO FOR NOW  I'M  GOING TO
 7       LEAVE IT OUT, BUT I WANT TO MENTION IT FOR THOSE
 8       PURISTS IN THE AUDIENCE WHO MAY GET VERY CONCERNED
 9       ABOUT THAT LATER,
10            THE QUALITY OF THIS TWO-ISOTOPE  THEORY
11       IS SHOWN IN THE NEXT SLIDE, WHICH LOOKS LIKE
12       A CALIBRATION CURVE OR A REGRESSION LINE THROUGH
13       A SERIES OF DATA POINTS, IS RATHER A  SERIES
14       OF DATA POINTS SHOWN IN THEIR RELATIONSHIP TO
15       THE LINE THAT THE MODEL PREDICTS,  As YOU  CAN
16       SEE, THEY FALL VERY, VERY CLOSE TO THAT LINE,
17       IN FACT, THEY'RE WITHIN EXPERIMENTAL  ERROR IN
18       ALL CASES,   I SHOULD POINT OUT THAT THIS SET  OF
19       DATA WAS ACQUIRED FOR AN AM I NO ACID DERIVATIVE,
20       WHICH HAS VERY LITTLE BEARING ON  US RIGHT  NOW,
21       BUT NEVERTHELESS HAD TO BE EXTRACTED,1  IT HAD  TO
22       BE DERIVATIZED AT BOTH ENDS OF THE MOLECULE,
23            ONE OF THOSE STEPS WAS A NONQUANTITATIVE
24       ESTERIFICATION,  F.VEN SO, THE DATA  FALLS VERY,
25
                                65

-------
    GABA  DATA vs  ISOTOPE DILUTION  THEORY
100
.01  —
                                                   m
                                                   vo
                        1         10


                        MOLE  RATIO
100

-------
 1       VERY NICELY ON THE LINE OR  NEAR  THE  LINE  THAT
 2       THE THEORY PREDICTS,
 3            THE THEORY, THEN, LOOKS VERY  PROMISING,
 4       AND THE QUESTION NOW BECOMES, WHAT ARE WE  GOING
 5       TO DO WITH ALL OF THAT?  WELL, LET'S SEE  IF
 6       WE CAN DETERMINE WHICH WAY  TO CALCULATE DATA
 7       THAT WE ACQUIRE ON REAL SAMPLES,  HE COULD GO
 8       AHEAD AND USE THAT BIG EQUATION  THAT WE HAD  IN
 9       THE LAST SLIDE AND PROBABLY DO PRETTY WELL,
10       BUT HOW WELL, AND DO WE REALLY NEED THAT?  V'ELL,
11       LET'S SEE WHAT THE SITUATION IS,
12            THE NEXT SLIDE SHOWS SOME OF THE EQUATIONS
13       THAT ARE FAIRLY COMMONLY USED,   THE MOST COMMON
14       ONE IS THIS VERY SIMPLE EQUATION WHICH SIMPLY
15       SAYS THAT THE MOLE RATIO OF SAMPLE TO INTERNAL
16       STANDARD IS DIRECTLY RELATED TO  THE ISOTOPE
17       RATIO THAT ONE MEASURES FROM THE MIXTURE,
18            THAT'S VERY EASY TO LIVE WITH,  IT MAKES
19       TWO ASSUMPTIONS:  ONE IS THAT THERE IS NO
20       UNLABELED MATERIAL IN THE INTERNAL STANDARD
21       TO BEGIN WITH,1 THE OTHER IS THAT THE UNLABELED
22       MATERIAL HAS NO NATURAL ABUNDANCE AT THE HIGHER
23       MASS M/Z,  CLEARLY THE UNLABELED MATERIAL  WILL
24       NOT HAVE VERY MUCH OF THE LABELED MATERIAL IN
25       IT,  THERE is A CERTAIN NATURAL  ABUNDANCE  OF
                                 66

-------
                                     CALCULATION  METHODS
                EQUATION                    ASSUMPTION               APPLICATION




          7"  Rm                          Rx—;  Ry-°          10Ry < Rm < '1Rx
          x   Rm(Rx  +  ])

          7=   Rx - Rm                   Ry-°                   10Ry

-------
 1       CARBON 1 AND CARBON 14 IN THE WORLD, AS WELL AS
 2       CARBON 12, AND THOSE ARE THINGS THAT THAT
 3       ASSUMPTION IS CONCERNED WITH, THOSE ABUNDANCES
 4       OF OTHER THINGS,
 5            WELL, THIS GETS A LITTLE BIT AHEAD OF
 6       OURSELVES HERE  (INDICATING), BUT THAT'S A RANGE
 7       THAT WE CAN DEFINE AS BEING APPLICABLE FOR THAT
 8       EQUATION, AND IT'S BASED ON THE WINDOW IN WHICH
 9       RM FALLS IN RELATION TO:  AT ONE END OF THE
 10       SCALE, THE ISOTOPE RATIO OF THE LABELED COMPOUND,
 11       AND AT THE OTHER END OF THE SCALE, THE ISOTOPE
 12       RATIO OF THE UNLABELED MATERIAL (INDICATING),
 13    .        IF WE REACH A POINT WHERE THIS ASSUMPTION
 14       IS NO GOOD—IN OTHER WORDS, WE GET TOO CLOSE
 15       TO RY OR RX~THEN WE HAVE TO MAKE A CORRECTION
 16       FOR THE AMOUNT OF MATERIAL THAT'S IN THERE,
 17            THIS EQUATION MAKES THAT CORRECTION, AND
 18       YOU CAN SEE THAT THERE ARE TWO DIFFERENT PLACES
 19       IN THE EQUATIONS WHICH HAVE AN P  VALUE IN THERE
                                        X
 20       TO CARRY OUT THAT PROCESS,  THERE IS AN EQUIVALENT
 21       SORT OF AN EQUATION WHEN THE MATERIAL THAT WE'VE
 22       PURCHASED SOMEWHERE AS A STANDARD HAS SOME
 23       ISOTOPIC IMPURITY IN IT, AND 1 JUST PUT THAT IN
 24       HERE ALSO BECAUSE WE MAY HAVE TO MAKE THAT CORRECTION,
25       THIS CORRECTION IS ONE THAT IS OFTEN MADE; THIS
                                 67

-------
1        CORRECTION IS ONE THAT IS SELDOM MADE ON A



2        FREQUENCY BASIS IN THE LITERATURE,



3             THE EQUATION HERE AT THE BOTTOM (INDICATING)



4        MAKES BOTH CORRECTIONS AND IS THE MODEL,  l»/E



5       JUST ASSUME THAT THOSE CORRECTIONS WILL BE CORRECT,



6       BUT AS YOU NOTICE OVER HERE, WE'RE NOT SAYING



7       THAT WE CAN DEAL WITH ALL OF THE DATA THAT IT



8       MIGHT BE POSSIBLE TO GENERATE, AND I'M GOING TO



9       SKIP ON TO THE NEXT SLIDE, I PRESUME LEAVING



10       MANY OF YOU  IN A BIT OF A CONFUSED STATE RIGHT



11       THERE, BUT I THINK HERE WE CAN SEE A LITTLE BIT



12       MORE CLEARLY WHAT I'M SAYING,



13            IN TERMS OF RYAND Rv, WE HAVE OVER HERE
                          A     Y


14       THE RATIO OF THE MIXTURE  (INDICATING) PLOTTED



15       FOR A HYPOTHETICAL COMPOUND WHICH HAS ISOTOPE



16       RATIOS OF 100 FOR RX AND  ,01 FOR  Ry,  THESE



17       ARE FAIRLY COMMON SORTS OF NUMBERS TO ENCOUNTER



18       WITH THIS METHOD, AND  IT  GIVES  US A  NICE



19       PICTURE TO DEAL  WITH,  AT ANY RATE,  WHEN WE



20       USE THE SIMPLE EQUATION,  X/Y  IS  EQUAL TO R^,



21       WE SAY WE CAN DEAL WITH THAT  IN  A WINDOW OF



22       VALUES DEFINED BY 10 TIMES  Ry,  AND GOING TO



23       ONE-TENTH OF RX,  YOU CAN  SEE THAT THAT  IS  A



24       VERY STRAIGHT  LINE HERE AND WE  DON'T NEED  TO



25

-------
VM
    00
                         ,001
,01
100
1000
                                                       X
                                                       Y

-------
1        .MAKE ANY CORRECTIONS,  1~HAT LINE IS SO CLOSE TO
2        THEORETICALLY CORRECT THAT WE DON'T NEED TO
3       WORRY ABOUT ANY ISOTOPIC INTERFERENCES THAT
4       MIGHT BE TAKING PLACE.  IN FACT, THE LINE THAT
5       IS SHOWN STARTS TO CURVE OUT, AND YOU CAN SEE
6       IT CURVING OUT VERY HEAVILY UP HERE (INDICATING),
7       BUT IT STARTS TO CURVE IN AN S-SHAPE RIGHT HERE
8       AT THE VERY CENTER POINT, OFF THIS WAY
9       (INDICATING), AND FROM THE CENTER POINT OFF  IN
10       THAT WAY (INDICATING) RIGHT IN THE BEGINNING,
11       BUT THE AMOUNT OF CURVATURE IN THAT REGION IS
12       VERY LOW, SO WE DON'T NEED TO WORRY ABOUT THAT,
13       THE ERRORS ARE GOING TO BE VERY, VERY SMALL.  As
14       WE START TO MOVE OUT  IN THE MOLE RATIO, NOW, TO A
15       POINT WHERE WE HAVE MORE AND MORE X RELATIVE TO Y,
16       WE START TO HAVE TO MAKE A CORRECTION FOR X, AND
17       AS WE DO THAT, WE CAN SEE WE'VE GOT MORE AND MORE
18       x  IN THERE, WE'VE GOT TO MAKE SOME KIND OF CORRECTION
19       FOR  IT,  $0 WE NOW GET  INTO A REGION WHERE WE'RE
20       CORRECTING FOR THIS  CURVATURE FOR RX HERE AND  Ry
21       DOWN HERE, DEPENDING  UPON WHICH ONE OF THOSE
22       EQUATIONS WE'RE DEALING WITH, AND AS WE DO THAT, WE
23       CAN MAKE THE CORRECTION,  BUT, AS CORRECTIONS  HAVE A
24       TENDENCY TO GO, THERE'S A LIMITING POINT AT  WHICH
25
                                  69

-------
 1       THE PROPAGATION OF ERRORS IN THAT CORRECTION STARTS
 2       TO OVERCOME THINGS AND WE REALLY OUGHT TO STOP,
 3       WE NEED TO MAKE SOME SORT OF PREDICTION AS TO WHAT
 4       THAT IS, AND I'LL SHOW YOU HOW THAT PREDICTION IS
 5       MADE,   WHAT IT TURNS OUT is THAT AT ABOUT ONE-HALF
 6       OF RX AT THAT END AND 2 Ry ON THAT END (INDICATING),
 7       AND BY GOING FROM THE MOST SIMPLE EQUATION, THEN,
 8       WHICH PUTS US ON THIS PART OF THE GRAPH (INDICATING),
 9       WE CHANGE FROM TWO ORDERS OF MAGNITUDE IN APPLICATION
10       TO ABOUT FOUR ORDERS OF MAGNITUDE IN APPLICATION,
11       AND WE'VE REALIZED IN THIS PARTICULAR SITUATION A
12       DOUBLING OF THE CONCENTRATION RANGE THAT WE CAN DEAL
13       WITH,   FOUR ORDERS OF MAGNITUDE IS PROBABLY BETTER
14       THAN ANYBODY'S GC/MS CAN DO ANYWAY, so THAT OUGHT TO
15       BE PLENTY,  TWO ORDERS WOULD BE NICEj WE COULD DEAL
16       IN HERE VERY EASILY,  WHAT WE'LL FIND OUT IS THAT
17       MANY OF THE P^'s AND Ry's THAT WE ENCOUNTER IN
18       PRACTICE ARE MUCH WIDER THAN THESE TWO THAT I'VE
19       SELECTED HERE,  THIS IS ALMOST ONE OF THE WORST
20       CASES (INDICATING), BUT EVEN IN A WORSE CASE, A
21       TYPICAL WORSE CASE, IT CAN WORK VERY NICELY,
22            THE FACT THAT IT CAN WORK IS SHOWN IN THE NEXT
23       SLIDE,  WHERE WE TOOK SOME DATA FOR SOME VOLATILE
24       COMPOUNDS WHERE WE HAD THE ABILITY TO SELECT M/E's
25
                                  70

-------
EFFECTS OF DATA REDUCTION METHOD ON QUANTITATION
COMPOUND
BENZENE


TOLUENE

1,2-DICHLOROETHANE




M/E's
78/84
50/56
77/82
92/100
91/98
62/67
64/67
98/104
49/53
98/102
M/E
SELECTION
FACTOR
4,79
3,91
3,79
8,29
7,72
8r94
7,92
6,19
5,73
2,73
DEVIATION FROM REGRESSION LINE (%)
ASSUMPTION
Rx—
RY— 0
10
10
39
7
9
9
14
28
11
54
RY— 0
10
10
37
10
9
10
14
28
11
69
RX-OO
10
28
40
10
12
10
14
28
11
69
	
9
23
36
10
12
9
11
18
16
36

-------
 1      FOR SEVERAL DIFFERENT MOLECULES  AND  THIS  VALUE
 2      HERE  (INDICATING),  I HAVE  SOMETHING  CALLED M/E
 3      SELECTION FACTOR AND THAT  IS VERY  CLOSE TO
 4      THE DIFFERENCE BETWEEN Ry  AND  Ry,  AND AS  RX AND
 5      RY GET WIDER AND WIDER.,  FURTHER  AND  FURTHER
 6      APART, WE SHOULD BE ABLE TO WORK WITH WIDER AND
 7      WIDER CONCENTRATION RANGES,
 8          ANYWAY.,  AS WE GO THROUGH THESE EQUATIONS WHERE
 9      WE HAVE THE SIMPLE EQUATION HERE (INDICATING)  AND
10      MOVING ACROSS TO THE MORE  COMPLEX  EQUATION,WHEN WE
n      HAVE A NUMBER HERE THAT SAYS,  THIS IS A FAIRLY
12      LARGE NUMBER (INDICATING), THEN  NO MATTER  HOW  WE
13      CALCULATE THE DATA, WE'RE  ON THAT  SEGMENT  OF THE
14      RM VERSUS X/Y CURVE THAT  IS A STRAIGHT LINE,  So
15      AS WE MAKE MORE AND MORE CORRECTIONS FOR THE
16      CURVATURE, WE DON'T REALLY SEE ANYTHING BECAUSE
17      THE STATISTICAL VARIATION  IN THE MEASUREMENTS
18      THEMSELVES REALLY DOESN'T  GIVE US  ANY NEW  DATA,
19          AS WE MOVE DOWN THE LINE,,,WELL, LET'S  MOVE
20      RIGHT TO THE BOTTOM HERE (INDICATING),  HERE WE
21      HAVE A SITUATION WHERE FAILING TO  MAKE CORREC-
22      TIONS RESULTS IN POOR DATA, BUT  WHEN WE MAKE ALL
23      OF THE CORRECTIONS, WE DO  APPRECIATE AN IMPROVE-
24      MENT,  AND YOU CAN SEE THAT THIS  VALUE HERE
25      (INDICATING)  is  A  SMALL  VALUE  COMPARED   TO  ALL

-------
1        OF  THE OTHERS,

2           I'M GOING TO TALK A LITTLE BIT MORE ABOUT WHAT


3        THIS FACTOR IS  LATER ON.  BUT WHAT I  WANT TO SAY IS
4
        THAT HERE ARE THREE COMPOUNDS; NO MATTER HOW WE
5

        CALCULATE IT, THE DATA COMES OUT REASONABLY WELL.
6

7       IN  EACH OF THESE CASES, THE VALUES THAT WE PREDICT


8       WOULD WORK BEST WOULD BE 78 OVER 8/J, AND YOU CAN


9       SEE THAT IN EACH ONE WE ALWAYS ARE PICKING OUT THE

10
        ONE THAT WORKS BEST AND SO IT SEEMS THAT WE AT
11
12
        LEAST HAVE FOUND OUT SOMETHING,  WE'RE TALKING
13       ABOUT PROPAGATED ERRORS, AND THOSE ARE REALLY WHAT

14
        WE'RE LOOKING AT IN THESE CALCULATIONS AND AS A
15
        RESULT I WANT TO JUST SHOW YOU A FEW LITTLE
16

17       PIECES OF ARITHMETIC HERE THAT GIVE US AN  IDEA


18       THROUGH THE MODEL WHAT  IS GOING TO HAPPEN,

19
           THE NEXT SLIDE SHOWS US WHAT THE PROPAGATION
20
        OF ERRORS LOOKS LIKE ON A MATHEMATICAL BASIS,
21
        THIS  IS YOUR BASIC PHYSICAL CHEMISTRY AT COLLEGE

        LEVEL AND THE MATHEMATICS GET A LITTLE INVOLVED

        AND THE EQUATIONS TEND  TO RUN ACROSS SEVERAL  PAGES,
24
        BUT IT ALL COMES DOWN TO SOMETHING THAT WE CAN AT
25
                                  72

-------
                                     PROPAGATION OF ERRORS
                   d(x/y)  =
                                3f(R
                                    I"
                                  3R
2   /9f(Rm)
  +  _ ^i—
                                                                               1/2
-
                              .
     WHERE
¥>>
     d(x/y)
      (x/y)
                                                                                        1/2

-------
1        LEAST GET OUR TEETH  INTO,   IT'S  JUST,  I  WANT  TO
2        SHOW YOU WHERE WE'RE  GOING,  HOW  WE'RE  GETTING
3       THERE, AND WHAT WE END UP WITH,  THE NEXT  SLIDE
4       SHOWS A PLOT OF PROPAGATED  ERROR VERSUS  THE MOLE
5       RATIO OF X/Y,  THE WAY THAT  WE PLOTTED THIS UP WAS
6       FOR EACH OF THE TERMS,  THERE'LL BE A  PROPAGATED
7       ERROR ASSOCIATED WITH THE ISOTOPE RATIO  OF THE
8       MIXTURE, A PROPAGATED ERROR  ASSOCIATED WITH THE
9       ISOTOPE RATIO OF THE NATURALLY ABUNDANT  MATERIAL,
10       AND ANOTHER ONE FOR THE ENRICHED MATERIAL  OR  THE
11       LABELED COMPOUND,  ALL THREE COMBINE TO  GIVE  THE
12       TOTAL PROPAGATED ERROR IN THE X/Y VALUE,   IT, AS
13       WE WOULD ASSUME, IS THE WORST LINE,' IT'S ALWAYS
14       THE HIGHEST LINE AND THAT MEANS  IT HAS THE HIGHEST
15       PERCENT ERROR,   THE Ry VALUE IS AFFECTING THE
16       DATA MOST AT POINTS IN THE CURVE WHERE THERE
17       IS RELATIVELY MORE Y THAN THERE IS X,   IN OTHER
18       WORDS, DOWN HERE WE START TO SEE THE PROPAGATED
        ERROR RISE, AND IT DOES RISE VERY QUICKLY AS  WE
        GET OUT HERE TO SOME CERTAIN POINT (INDICATING),
        THE OTHER DIRECTION,  WE COME DOWN ASYMPTOTICALLY;
        THERE'S  VERY LITTLE Y WITH RESPECT TO x OUT HERE
        AT 1,000 (INDICATING), AND AS A RESULT, THE QUANTITY
        OF Y THAT'S  PRESENT HAS VERY LITTLE' BEARING ON THE
24       AMOUNT OF ERROR  THAT  IT CREATES,   THE RX SITUATION
        IS JUST  EXACTLY  LIKE  THIS ONE,  BUT A MIRROR IMAGE OF
                                  73
19

20

21
22

23

-------
    18
    16-
    14-
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10-
 8-
     6-
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     0
                                               d(X/Y)
                                                 X/Y
         ,001
                    ,01
,1
 1

X/Y
10
100
                                                                                                     en
1000

-------
1        IT AND FOR THE SAME REASON; AS WE GET MORE AND MORE
2       X IN THERE, THE IMPACT THAT THAT HAS ON THE ERROR
3       BECOMES GREATER AND GREATER AND AT SOME POINT OUT
4       HERE (INDICATING) WE'VE GOT TO CALL A HALT TO WHAT
5       WE'RE DOING BECAUSE THE PROPAGATED ERROR JUST
6       SKYROCKETS,
7          AT ANY RATE, THE RM VALUE, IN OTHER WORDS,
8       THE NUMBERS THAT WE'RE MEASURING IN THE MIXTURE
9       OF THE TWO, THE SAMPLE THAT WE'RE ACTUALLY GOING
10       TO GET OUR DATA FROM, SEEMS TO FAIRLY CLOSELY
11       APPROXIMATE THE ULTIMATE ERRORS THAT WE SEE IN
12       THE RATIO OF SAMPLE TO INTERNAL STANDARD AND
13       YOU CAN SEE, WE'VE GOT A LIGHT CURVE HERE AND A
14       DARKER CURVE HERE, AND AS A RESULT, IT SEEMS
15       REASONABLE TO MAKE SOME GUESSES BASED ON THIS TERM
16       IN THE PROPAGATED ERROR EQUATION TO SEE IF WE CAN
17       SAY, WHERE SHOULD WE STOP WHEN WE MOVE OUT HERE?
18       WE HAVE TO DRAW A LINE SOMEWHERE,1 WHERE ARE WE GOING
19       TO DRAW THAT LINE AND NOT GO ANY FURTHER?  As A
20       RESULT, WE WILI	WELL I'M GOING TO SHOW YOU SOME
21       MORE ARITHMETIC  IN THE NEXT  SLIDEj WE CAN DO THAT
22        KIND OF THING MATHEMATICALLY BY SUBSTITUTING IN
23       FOR THE DX/Y OVER X/Y,  J'N OTHER WORDS, WE'RE GOING
24       TO SAY THE PERCENT ERROR  IS  TWICE THE MEASUREMENT
25
                                 74

-------
                                      M/E  SELECTION
SAY THAT ACCEPTABLE RESULTS  HAVE AN  ERROR  EQUAL TO TWICE THE ERROR IN THE RM MEASUREMENT
d(x/v) . 0 ***_    (Rx - V dR
               2
                                     m
F°R  ('lax'  "**  Rx-dRy«  Rm   SO:         R^ 1 RX
FOR         :   R>>  RandR>:>  R    S0:
CONCENTRATION RANGE FOR SUCCESSFUL APPLICATION  IS GIVEN BY:
                                  •   
-------
1        ERROR IN MEASURING THE ISOTOPE RATIO OF THE
2       MIXTURE,  THESE RUN AROUND 5 PERCENT OR so,  So
3       WE'RE GOING TO SAY/ FOR NOW, in PERCENT ERROR
4       WE'LL LIVE WITH; ANYTHING WORSE THAN THAT  is NO
5       GOOD,  WHERE is PROPAGATED ERROR GOING TO GO FROM
6       LESS THAN 10 PERCENT TO GREATER THAN 10 PERCENT?
7       WELL, IT DOES THAT ON BOTH ENDS OF THE CURVE.  IT
8       DOES THAT ON THE X/Y MAX END AND ON THE X/Y MIN
9       END,  THESE SITUATIONS EXIST, AND WHEN THAT HAPPENS,
10       YOU CAN GO THROUGH THIS EQUATION, AND WE COME OUT
n       SAYING  THAT IF  RM  IS APPROXIMATELY EQUAL TO HALF
12       OF  Rx,  THAT'S THE  CROSSOVER POINT,  So AS  LONG
13       AS  WE STAY WITH RM'S THAT ARE LESS THAN HALF OF
14       RX, WE'LL BE  IN BAD SHAPE,
15            AT THE OTHER  END, AT THE MINIMUM END, THE
16       SITUATION COMES OUT THAT RM SHOULD BE GREATER
17       THAN 2  Ry,  THIS  IS THE CROSSOVER POINT, SO AS
18       LONG AS WE STAY WITH  RM'S THAT ARE GREATER THAN
19       2  Py, THEN THE  MODEL  SHOULD HOLD AND WE SHOULD
20       GET GOOD DATA,  IF WE TAKE THE DIFFERENCE  BETWEEN
21       THE MAX AND THE MIN—AND REMEMBER WE DID THIS ON
22       A  LOG SCALE BECAUSE WE'RE LOOKING AT PERCENT
23       THINGS—AND SUBSTITUTE  INTO OUR  FULL EQUATION THE
24       VALUES  ONE-HALF RX AND 2 Ry  IN THE APPROPRIATE
25
                                  75

-------
 1       PLACES, WE COME UP WITH THIS EXPRESSION,  AND  IT
 2       MERELY SAYS THAT FOR THE WIDEST CONCENTRATION
 3       RANGE OF APPLICATION, WE SHOULD SELECT M/E'S
 4       THAT GIVE US THE LARGEST NUMBER FOR THE  LOG OF
 5       RX/RY,  THAT'S A PRETTY SIMPLE PLACE TO  COME TO
 6       AFTER ALL OF THAT ARITHMETIC,
 7            THE SELECTION OF M/E'S, THEN, CAN BE DONE
 8       FAIRLY SIMPLY BY JUST LOOKING AT THE RATIO OF
 9       THE ISOTOPE RATIOS,  WHEN THAT NUMBER IS  LARGE,
10       THEN WE WILL HAVE A WIDE RANGE BETWEEN
11       CONCENTRATIONS AT THE CUTOFF POINTS,  THIS PART
12       OF THE MODEL ONLY TAKES INTO ACCOUNT THE  FACT
13       THAT WE'RE GOING TO MAKE A MEASUREMENT AND THAT
14       THE PRECISION OF THAT MEASUREMENT  IS UNRELATED
15       TO ANYTHING; THAT'S NOT TRUE,
16            THE PRECISION OF THE MEASUREMENTS IS
17       RELATED TO THE ABSOLUTE AMOUNT OF  SIGNAL  WE CAN
18       GET, BASED ON WHAT THE ABUNDANCE OF THE  IONS
19       OR THE M/E THAT WE'RE MEASURING IS,  IF WE
20       ARE LOOKING AT A PNA WHERE YOU'VE  GOT MAYBE
21       80 PERCENT OF THE TOTAL IONIZATION IN THE PEAK
22       THAT THE MEASUREMENT WILL LIKELY BE MADE  AT,
23       THAT WILL PROVIDE MORE PRECISE DATA THAN  WILL THE
24
25
                                 76

-------
1        DATA THAT ONE WOULD ENCOUNTER FROM, SAY, DIMETHYL-
2       NITROSAMINE, WHICH DOESN'T GIVE US  TOO  MUCH  SIGNAL
3       FROM A MASS SPEC STANDPOINT,
4         AS A RESULT, WE PLAYED AROUND A  LITTLE BIT, AND
5       I ADMIT THIS  IS A LITTLE EMPIRICAL, BUT THE NEXT
6       SLIDE GIVES US A LITTLE CORRECTION FACTOR,  AN
7       EMPIRICAL FACTOR, TO TAKE INTO ACCOUNT THE  EFFECT
8       THAT ABUNDANCE WILL HAVE ON THE SELECTION OF M/E'S,
9       THE VALUE THAT WE CAME UP WITH A CORRECTION
10       BASED ON THE  LOG OF 2 OVER THE ABUNDANCE OF THE
11       MORE ABUNDANT ISOTOPE IN THE UNLABELED COMPOUND
12       PLUS THE ABUNDANCE OF THE MORE ABUNDANT ISOTOPE
13       IN THE LABELED COMPOUND,  THE LESS ABUNDANT OF
14       THE TWO WE'RE NOT GOING TO WORRY ABOUT BECAUSE
15       WE'VE ALREADY SAID WE'RE GOING TO  BE  IN A WINDOW,
16       AND WHEN WE'RE IN THAT WINDOW THE  AMOUNT OF SIGNAL
17       THAT WE SEE IS GOING TO BE BASED ON THE TWO MORE
18       ABUNDANT ISOTOPES AND NOT BE VERY  MUCH AFFECTED
19       BY THE TWO LESS ABUNDANT ISOTOPES,  V/HEN WE PUT
20       ALL OF THAT TOGETHER, WE HAVE A TERM THAT WE'RE
21       CALLING AN M/E SELECTION CRITERIA,   IT  IS AFFECTED
22       VERY, VERY MUCH BY THE LOG OF RX OVER  Ry.   IT
23       IS AFFECTED MUCH, MUCH LESS BY THIS OTHER TERM,
24       THIS MAY CHANGE FROM l\ TO 12, SAY, WHEREAS  THIS
25       HARDLY EVER REACHES A NUMBER LARGER THAN TWO,
                                  77

-------
  ION ABUNDANCE IN M/E SELECTION
 EMPERICAL FACTOR = -LOG
      M/E SELECTION CRITERIA
MAXIMIZE

-------
1        AND NORMALLY,  IT'S CLOSER TO 1,2 OR SOMETHING
2        LIKE THAT,
3          THE NEXT SLIDE SHOWS US, REALLY, THAT THIS M/E
4        SELECTION CRITERIA DOES HAVE SOME REASONABLE EFFECT
5       ON WHAT THE DATA LOOKS LIKE THAT WE END UP WITH
6       FOR THE COMPLICATED EQUATION,  WHAT WE DID WAS,,,
7       THESE ARE THE SAME M/E 'S THAT .WE HAD BEFORE WHERE WE
8       GOT OUR FACTOR UP HERE (INDICATING), SELECTION
9       CRITERIA.  THIS IS A CORRELATION COEFFICIENT OF  THE
10       DATA THAT WE OBTAINED  FOR A SERIES OF SAMPLES RUN
11       FROM ABOUT 1 TO 1,000  MICROGRAM PER LITER LEVEL  AND
12       WE HAD BETWEEN 5 AND 7 DATA POINTS PER CORRELATION
13       COEFFICIENT,  OVER HERE  IS A MEAN DEVIATION  (INDICATING)
14       FROM THE REGRESSION LINE, WHICH  IS ROUGHLY PERCENT
15       ERROR, IF YOU WILL.  WHAT WE'RE  PREDICTING IS THAT,
16       AS WE  ORDER FROM  LARGE TO SMALL, BEST TO WORST,  WE
17       WILL GET ON ANY GIVEN  COMPOUND  THE SAME ORDER  IN
18       PERCENT  ERROR AND THAT'S WHAT WE  SEE,  WE SEE  IT
19       FOR BENZENE, WE SEE  IT FOR TOLUENE, WE SEE  IT  FOR
20       DICHLOROTHANE,: AND HERE WE'RE GOING FROM A VERY  LARGE
21       NUMBER DOWN TO  REALLY  A  VERY SMALL NUMBER
22       (INDICATING),   You CAN SEE THAT THAT  FOLLOWS,
23       THERE'S  A  LITTLE  INVERSION HERE (INDICATING),  BUT
24       THERE'S  NOT MUCH  DIFFERENCE  IN  THESE  FACTORS THAT
25       WE'RE  LOOKING AT  OVER  HERE, EITHER (INDICATING),
                                 78

-------
                                EFFECTIVENESS OF M/E SELECTION CRITERIA
COMPOUND
BENZENE


TOLUENE

1,2-DICHLOROETHANE




M/E's
78/84
50/56
77/82
92/100
91/98
62/67
64/67
98/104
49/53
98/102
loa/Rx\ loa/ 2 \
°9lV 109lax+V
4,79
3,91
3,79
8,19
7,72
8,94
7,92
6,19
5,73
2,73
CORRELATION
.COEFFICIENT
,998
,994
,981
,999
,998
,998
,997
,993
,997
,975
MEAN DEVIATION
FROM REGRESSION
LINE (%)
9
23
36
10
12
9
11
18
16
36
00

-------
1        SO I'M NOT REALLY TOO CONCERNED ABOUT THAT,
2       ANYWAY,  IT LOOKS LIKE WE'VE COME UP WITH A WAY
3       TO PICK M/E'S ON A SYSTEMATIC BASIS,
4            IT SEEMS THAT WE'VE GOT SOME CRITERIA NOW
5       FOR SELECTING THE CALCULATION METHOD, OR AT LEAST
6       WHICH ONE WE CAN USE AND WHEN, AND THERE IS REALLY
7       ONE OTHER THING THAT WE CAN COME UP WITH WITH
8       THIS MODEL, AND COME UP WITH IT FAIRLY EASILY,
9       AND THAT IS MAKING A PREDICTION OF HOW WE'RE
10       GOING TO STANDARDIZE OUR SPIKING SOLUTION,  IT'S
11       A.LSO RELATED TO HOW MUCH MATERIAL WE SHOULD THEN
12       SUBSEQUENTLY SPIKE INTO OUR SAMPLES,
13            IF WE TAKE THE SECOND DERIVATIVE OF THE
14       MODEL EQUATION WITH RESPECT TO,,,AND THE NEXT
15       SLIDE HAS THAT IN  IT,,,WITH RESPECT TO THE
16       ERRORS THAT WE SEE IN RM, THAT BEING THE PARAMETER
17       THAT AFFECTS THE RESULTS MORE THAN ANYTHING ELSE,
18       WE CAN CRUNCH THROUGH THIS HORRIBLE MOUNTAIN OF
19       PAPERWORK AND COME UP WITH A VERY SIMPLE EXPRESSION
20       THAT SAYS THAT THE BEST SITUATION IS GOING TO
21       BE THE MEASUREMENT WHICH TAKES  PLACE FOR AN
22       RM WHICH  IS EQUAL  TO THE SQUARE  ROOT OF THE
          M
23       PRODUCT OF Rx TIMES Ry,  IN OTHER WORDS, WE CAN
24       PREDICT THE BEST R^j WE CAN THEN TAKE THIS R^, STICK
25       IT BACK  IN THE EQUATION, AND  CALCULATE THE BEST

-------
                                 QUANTITY OF LABELED MATERIAL TO ADD
                                            d2(x/y)/(x/y)
VO


                                WHEN
                                             R   -  fR  R  ^/2
                                             Km  "  
-------
 1       X/Y,   THIS TURNS OUT TO BE RIGHT AT THE CENTER
 2       OF THE STRAIGHT SECTION OF THE CURVE, SO YOU
 3       CAN PRETTY MUCH SAY THATX/Y IS EQUAL TO RM-
 4       WHATEVER RM TURNS OUT TO BE, BASED ON THIS EQUATION,
 5       THAT'S WHAT WE SHOULD USE AS A RATIO FOR
 6       CALIBRATING OUR INTERNAL STANDARD,  IF WE HAVE
 7       NO INFORMATION AHEAD OF TIME, SUCH AS WITH
 8       SAMPLES, WE CAN PREDICT A CONCENTRATION RANGE
 9       AND SHOOT FOR THE MIDDLE OF THAT RANGE,  HE
10       KNOW THAT RANGE BASED ON GUESSES, BUT WE CAN
'11       MAKE THOSE GUESSES AND HAVE A GO AT IT; THEN
12       AT LEAST WE'LL BE DIRECTING OUR EFFORT IN
13       SOME FORM,
14            THE NEXT SLIDE JUST SUMMARIZES THE THREE
15       SIGNIFICANT THINGS THAT I'VE GONE THROUGH SO
16       FAR,   THE SELECTION OF M/E's BASED ON THIS
17       FACTOR, THE CALCULATION METHOD, AND I'VE ONLY
18       INCLUDED TWO OF THEM BECAUSE IT JUST SEEMS TO
19       ME THAT THERE'S LITTLE REASON TO USE THE OTHER
20       TWO,   MORE OFTEN THAN NOT, THIS ONE IS ADEQUATE;
21       IT'S THE HEIGHT OF SIMPLICITY, AND IT'S EASY TO
22       DETERMINE WHEN TO USE IT,  HE CAN USE IT WHEN
23       RM IS BETWEEN THESE TWO VALUES OF RX AND Ry
24       WE ALWAYS WILL KNOW THESE AHEAD OF TIME,  RX
25
                                 _80_

-------
                                   SUMMARY OF METHODOLOGY




                   BEST M/E's


                        MAXIMUM  LOG IK*- 1  - LOG ( -—f-g-J
g                  CALCULATION METHOD
                        y- = R*                 when  10Ry < Rm < '1Rx
(R  • R)(R
                           y    m   -x
                        x
                          =                    when  2R  < R  " -5R
                   BEST MOLE RATIO FOR STANDARDIZATION
                        J  where  Rm = (RyRy)1/2

-------
1        NEVER  CHANGES,  AND Ry's VALUE WAS FOR THE
2        MATERIAL THAT EITHER WE PURCHASED OR SOMEONE
3       GAVE us (INDICATING),
4            IF RM FALLS OUTSIDE OF THAT RANGE, WE USE
5       THIS OTHER EQUATION, BUT AGAIN, THERE ARE
6       LIMITATIONS,  AND AS LONG AS WE DON'T FALL OUTSIDE
7       OF THAT, WE CAN EXPECT THE RESULTS WILL BE
8       FAIRLY GOOD,   THE MOLE RATIO FOR STANDARDIZATION
9       IS THE ONE WE JUST SAW A MINUTE AGO, AND I
10       WON'T GO THROUGH THAT AGAIN,
11            THE PROOF, OF COURSE, IS  IN THE APPLICATION,
12       AND THE NEXT SLIDE SHOWS SOME  RESULTS WE GOT
13       FOR SOME PURGEABLES  IN LABORATORY PURE WATER
14       AND SOME SOAP SOLUTIONS,  WE MADE THE SAMPLES
15       AND WE KNOW HOW MUCH IS IN THEM, SO WE CAN
16       COME UP WITH PERCENT ERRORS,   !JHEN WE USE
17       STANDARD ADDITIONS, WHICH IS REALLY THAT
1«       CALCULATION THAT WE WERE LOOKING AT EARLIER
19       THIS MORNING, THE RESULTS COME OUT LOOKING
20       SOMETHING LIKE THIS  FOR THOSE  SAMPLES (INDICATING),
21            THE PURE WATER  IS NOT TOO BAD,1 THE SOAP
22       SOLUTIONS CAN GET PRETTY OUTRAGEOUS,  PURGING
23       SOAP SOLUTION IS NOT THE EASIEST THING IN THE
24
25

-------
                                             APPLICATION
SAMPLE
LABORATORY PURE WATER


SOAP SOLUTION
(HEAT)

SOAP SOLUTION
(SURFACTANT)

COMPOUND (DATA POINTS)
BENZENE (5)
TOLUENE (6)
L2-DICHLOROETHANE (4)
BENZENE (5)
TOLUENE (5)
1,2-DICH,LOROETHANE (V
BENZENE (5)
TOLUENE (4)
1,2-DICHLOROETHANE (4)
MEAN % ERROR
STANDARD ADDITION
31
21
51
62
87
92
.59
84
108
MEAN % ERROR
ISOTOPE DILUTION
27
23
17
23
17
26
24
44
58
oo

-------
1       WORLDj  WE  ASSUMED  THAT WE  WOULD HAVE PLENTY OF
2       MATRIX  EFFECTS,
3             AT THE  SAME TIME, WE  GOT SOME RESULTS,
4       WHEN  WE COMPARE THESE WITH THE ERRORS THAT WE
5       SEE WITH ISOTOPE DILUTION, WE SEE THAT WHEN IT
6      COMES OUT  WELL OVER HERE,  IT STILL COMES OUT
7      WELL  OVER  HERE (INDICATING), BUT WHEN IT COMES
8      OUT BAD OVER HERE, IT STILL COMES OUT WELL
9      OVER  HERE, AND THAT'S FAIRLY CONSISTENT UNTIL
10      ALL  OF  A SUDDEN  WE START TO HIT A SNAG DOWN
n       HERE  (INDICATING),
12            WELL, WE'RE  BACK TO A PROBLEM THAT is
13       NOMINALLY INSURMOUNTABLE,   WE'VE ADDED SOMETHING
14       TO THE  SOAP SOLUTION; WE ADDED A SURFACTANT
15       WITH  THIS SERIES OF SAMPLES, AND THAT SURFACTANT
16       ENDED UP  INTERFERING WITH THE ANALYSIS,   IF
17       WE'VE GOT INTERFERENCES, THE ONLY WAY WE  CAN
18       BEAT THEM IS TO GET RID OF THEM,  THERE ARE NO
19       TRICKS; IT'S A VERY SIMPLE CONCEPT,  WE JUST
20       DON'T ALWAYS KNOW HOW TO  DO  IT,  So  I WANT TO
21       POINT THIS OUT:    ISOTOPE  DILUTION METHOD  WON'T
22       OVERCOME  INTERFERENCES,   IF THERE  IS AN  INTER-
23       FERENCE TO DEAL WITH,  IT  JUST  HAS THE SAME PROBLEMS
24
25
                                 _82_

-------
 1       AS ANY OTHER METHOD,  WHEN THERE AREN'T
 2       INTERFERENCES, THE PRECISION  IS HIGH  AND  THE
 3       ERROR IS LOW,
 4            IF WE LOOK AT ANOTHER SET OF DATA., THIS
 5       TIME FOR SOME PQTW SAMPLES, AND FOR A LARGER
 6       GROUP OF COMPOUNDS, WE FIND THAT THE  ERROR  FOR
 7       STANDARD ADDITIONS CAN GET VERY HIGH,  FOR
 8       PHENOL, WE ENDED UP PREDICTING A NEGATIVE
 9       CONCENTRATION, AND RATHER THAN INCLUDE IT,  I
10       DECIDED TO IGNORE  IT,  AT THE SAME TIME,
n       SOMETIMES WE HIT A VALUE SPOT ON , AND THEN
12       THERE ARE OTHERS THAT ARE JUST TERRIBLE,
13            WITH ISOTOPE DILUTION, WE NEVER  LOSE ANY
14       DATA; WE NEVER GET ANY BAD ERROR SITUATIONS
15       WHETHER WE'RE LOOKING AT LAB WATER, RAW SEWAGE
16       OR TREATED SEWAGE,  PAW SEWAGE IS NOT THE NICEST
17       MATRIX THAT  I'VE EVER DEALT WITHj THERE'S A LOT
18       OF PARTICULATE MATERIAL IN IT, THERE'S A  LOT
19       OF STUFF IN  IT,  THE EFFLUENT IS A LOT CLEANERj
20       THE PERCENT  ERRORS ARE UNIFORMLY LOW,  AROUND
21       15 PERCENT,  WITH STANDARD ADDITION,  THEY RUM
22       AROUND 45 PERCENT  (INDICATING),
23            NOW, A  LITTLE BIT ABOUT HOW WE DID THIS,
24       SINCE I'M TALKING PERCENT ERROR AND REAL  SAMPLES,
25

-------
                                              APPLICATION

COMPOUND
BENZENE
TOLUENE
METHYLENE CHLORIDE
PHENOL
1,2-DICHLOROBENZENE
NAPHTHALENE
NITROBENZENE
CHRYSENE
BENZO(a)PYRENE
MEAN
PERCENT ERROR
STANDARD ADDITIONS*
LAB
WATER
11
31
39
133
71
0
2010
49
42
265(47)
POTW
INFLUENT
11
31
38
212
52
18
6
81
72
56
POTW
EFFLUENT
11
44
52
***
42
47
34
23
11
33

LAB
WATER
14
17
13
7
23
26
26
9
~" 14
17
ISOTOPE DILUTION
**
POTW POTW
INFLUENT EFFLUENT
4
6
11
8
21
41
5
14
, 24
15
9
11
8
4
22
27
18
7
7
13
00
LO
           *  ONE DATA  POINT PER ENTRY

          **  TWO DATA  POINTS PER ENTRY

             UNDEFINED;  NEGATIVE CONCENTRATION
***

-------
 1            WE GOT THIS INFORMATION BASED ON  THREE
 2       RUNS:  ONE OF THE AS-ACQUIRED SAMPLE,  ONE  OF
 3       THE AS-ACQUIRED SAMPLE SPIKED WITH 100 MICROGRAMS
 4       PER LITER OF THESE COMPOUNDS, PLUS A THIRD RUN
 5       SPIKED WITH 1,000 MICROGRAMS PER LITER,  FOR
 6       STANDARD ADDITIONS, WE TOOK THE DATA POINT FOR
 7       THE UNSPIKED SAMPLE AND SUBTRACTED IT  AS A
 8       BACKGROUND LEVEL FROM VALUE THAT WE GOT FOR THE
 9       100 MICROGRAM PER LITER SAMPLE.  WE KNOW WE
10       PUT 100 MICROGRAMS IN, SO WE SHOULD HAVE GOTTEN
'11       100 MICROGRAMS BACK,  PERCENT ERROR IS BASED
12       ON HOW MUCH OF THE 100 MICROGRAMS PER  LITER WE
13       GOT BACK,  SO WE REALLY DO KNOW THE PERCENT
14       ERROR THERE,
15            WE NEEDED THE 1,000 MICROGRAM PER LITER
16       SAMPLE WITH STANDARD ADDITIONS TO CARRY OUT
17       THE STANDARD ADDITIONS CALCULATION BECAUSE TWO
18       DATA POINTS ARE REQUIRED TO PRODUCE ONE
19       CONCENTRATION VALUE,  FOR THE ISOTOPE  DILUTION,
20       WE USED THE SAME PROCESS; THAT IS, WE  SUBTRACTED
21       THE BACKGROUND CONCENTRATION OF THE UNSPIKED
22       SAMPLE FROM THE VALUE DETERMINED FOR THE SPIKED
23       SAMPLE, AND CALCULATED OUR PERCENT ERROR BASED
24
25
                                J&4

-------
 1       ON THE RECOVERED CONCENTRATION OF OUR SPIKE,



 2       THE DATA OVER HERE (INDICATING)  IS BASED ON



 3       THE PERCENT ERROR FOR BOTH THE 100 AND THE



 4       1,000 MICROGRAM PER LITER VALUE,  WE'VE GOT



 5       TWICE AS MUCH DATA INVOLVED  IN THIS SERIES



 6       OF PERCENT ERRORS AS WE DO OVER  HERE  (INDICATING),



 7       BUT AT THE SAME TIME, THE ERROR  VALUES ARE



 8       ALWAYS LOW,  THEY AVERAGE ABOUT  15 PERCENT HERE,



 9       ABOUT 45 PERCENT HERE (INDICATING), ABOUT A



 10       FACTOR OF 3,  VIlTH ISOTOPE DILUTION,  WE GOT



'11       TWICE AS MUCH DATA FROM THE  SAME SET  OF RUNS,



 12             IF WE EXTRAPOLATE THAT  BACK TO COST PER



 13       SAMPLE, IT COSTS US HALF AS  MUCH TO RUN AN



 14       ISOTOPE DILUTION SAMPLE AS  IT DOES TO RUN A



 15       STANDARD ADDITION  SAMPLE,   IF WE ARE  SPIKING



 16       AND  CARRYING OUT STANDARD ADDITIONS-TYPE



 17       MEASUREMENTS TO A  LARGE DEGREE,  OR  IF WE'RE



 18       DOING A LOT  OF  SPIKING AND  RUNNING OF SPIKED



 19       PLUS UNSPIKED  SAMPLES, WE  COULD SAVE  HALF  OF



 20       THAT MONEY BY  USING  ISOTOPE  DILUTION,  THIS



 21        IS BECAUSE ALL  OF  THE  SPIKING TAKES  PLACE  IN



 22       THE  SAME  SAMPLES THAT  ARE  BEING ANALYZED,   $0



 23       WE'VE COVERED  THE  SAME  INFORMATION  BASE THAT
24




25
                                  85

-------
 1       THE SPIKING COVERS, BUT WE'VE  COVERED IT IN
 2       THE SAME SAMPLE MEDIA,
 3            THESE APPLICATIONS SEEM TO  PREDICT THAT
 4       WE'LL GET BETTER DATA AND WE'LL  GET  IT AT A
 5       LOWER COST BY USING ISOTOPE DILUTION  RATHER
 6       THAN STANDARD ADDITION,  THE DISADVANTAGES
 7       ARE MOSTLY ASSOCIATED WITH ROUTINE APPLICA-
 8       TION OF NEW TECHNOLOGY TO ENVIRONMENTAL-
 9       TYPE SAMPLES,
10            IN THE PAST, AS I MENTIONED EARLIER,  IT'S
11       TYPICALLY BEEN APPLIED TO DETERMINE ONE COMPOUND
12       PER ANALYSIS, AND WHAT WE'RE TALKING  ABOUT HERE
13       IS POTENTIALLY '\7 COMPOUNDS VMTH THE  BASE/
14       NEUTRAL FRACTION,  WELL, WE'RE TRYING TO  DO
15       47 COMPOUNDS THERE, ANYWAY, AND  WE GET MOST
16       OF THEM, SO IT SEEMS PROMISING,
17            WE DON'T KNOW WHAT'S GOING  TO HAPPEN  IN
18       ALL ENVIRONMENTAL SAMPLE SITUATIONS,   WE  DON'T
19       KNOW WHAT ALL THE INTERFERENCES  MIGHT BE,  BUT
20       WE DON'T KNOW THAT ANYWAY,  WE DO KNOW THAT
21       WE HAVE INTERFERENCES THE WAY WE  ANALYZE  NOW,
22       AND I'M SURE THERE WILL BE NEW ONES AS WE  LOOK
23
24
25
                                86

-------
               SUMMARY OF ISOTOPE DILUTION METHOD
ADVANTAGE
     1,  BETTER DATA
     2,  LOWER COST
DISADVANTAGE
     1,  NEW TECHNOLOGY FOR ROUTINE APPLICATIONS
     2,  NOT DEMONSTRATED FOR LARGE NUMBER OF ENVIRONMENTAL
         SAMPLE SITUATIONS

-------
 1       AT ADDITIONAL TYPES OF SAMPLES,
 2            THE INTERESTING THING WITH  ISOTOPE
 3       DILUTION IS THAT IF WE DON'T MAKE  IT AT ONE
 4       SET OF M/E'S, WE MIGHT MOVE TO A SECONDARY
 5       SET OF M/E'S AND CHECK OUR CONCENTRATION
 6       CALCULATION,  IF WE GET THE SAME NUMBER FROM
 7       TWO DIFFERENT M/E VALUES, THAT'S PRETTY CON~
 8       VINCING THAT THERE'S NO INTERFERENCE AT
 9       EITHER OF THEM,  IT'S NOT A GUARANTEE, BUT IT'S
10       PRETTY CLOSE TO IT,
11            THE WAY WE PLAN TO GO IN THE  FUTURE WITH
12       THIS WORK IS TO BUY SOMETHING LIKE 40 ADDITIONAL
13       LABELED COMPOUNDS,   WE'LL USE THESE IN LOOKING
14       AT MORE INDUSTRIAL SAMPLES,  THERE WILL ALSO
15       BE A COUPLE OF LABS OTHER THAN OURS GETTING
16       INVOLVED,  WE HOPE TO FIND THAT WHAT HAS WORKED
17       IN THE PAST FOR THE BIOLOGIST WILL ALSO WORK
18       FOR THE ENVIRONMENTAL CHEMIST,   I  HOPE WE'LL
19       HAVE A LOT MORE GOOD INFORMATION FOR ANOTHER
20       MEETING LIKE THIS,  SHOULD WE EVER  HAVE ONE,
21            IF THERE ARE ANY QUESTIONS, I WOULD BE
22       PLEASED TO TRY TO ANSWER THEM,
23
24
25
                                  87

-------

-------
                         QUESTION AND ANSWER
                              SESSION
 2
 3                                MR, OLLISON:  WILL OLLISON,
 4      A.P.I,   TWO QUESTIONS,  ONE, YOU DIDN'T SAY ANYTHING
 5      ABOUT WHEN AND WHERE YOU SPIKE YOUR SAMPLES,   I WAS
 6      WONDERING PARTICULARLY ABOUT EQUILIBRATIONS OF
 7      YOUR ISOTOPIC SPIKED WITH THREE-PHASED SAMPLES,
 8                                DR, COLBY:  WE SPIKED THE
 9      POTW SAMPLES, THE EXTRACTABLES, ABOUT ONE-HALF HOUR
10      PRIOR TO STARTING THE EXTRACTION,  THEY WERE SPIKED
11      IN THE CONTINUOUS LIQUID/LIQUID EXTRACTOR AND STIRRED
12      BEFORE ADDING METHYLENE CHLORIDE AND ADJUSTING THE
                                 MR, OLLISON:  Do YOU HAVE
14
1t.         ANY IDEA OF THE EQUILIBRATION TIMES INTO SOLID
I O
16         PHASES?
17                                DR, COLBY:  No, BUT IF WE
18
          BLEW IT, IF WE WAITED LONGER, WE'D DO EVEN BETTER,
19
2o         WOULDN'T WE?
21                                MR, OLLISON:  THE SECOND
          QUESTION WOULD BE, YOU MENTIONED ONLY FLUORANTHENES
          AS A POLYCYCLIC WITH EXCHANGE,  I SEEM TO RECALL
23
24         LAST YEAR THERE WAS SOME EXCHANGE WITH THE
          Dm ANTHRACENE.
25
                                 DR, COLBY:  THAT'S NOT

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1        EXCHANGE  PER SE.   I  BELIEVE  THAT'S USUALLY CONSIDERED
2       OXIDATION,   I THINK THAT  WHAT WAS TALKED ABOUT WAS
3       D]Q  ANTHRACENE BEING  OXIDIZED TO Dg  ANTHRAQUINONE,
4                                 MR,  OLLISOfl:   THAT MIGHT
5       BE MY MISTAKE,   IT  WAS  SOMETHING THAT  WOULD DO WITH
6       THE GLASS WOOL,
7                                 m. CLAEYS:    BOBCLAEYS, WITH
8       THE NATIONAL COUNCIL,  BRUCE,   DID YOU  BRING ALONG ANY
9       OF YOUR  EXCHANGE DATA FOR CHLOROFORM?
10                                 DR,  COLBY:  I THINK I MAY
11       HAVE SOME OF IT,
12                                 MR,.CLAhYS:    CAN YOU GIVE us A
13       ROUGH  IDEA  OF  HOW FAST  SOMETHING LIKE  THAT WOULD
I4       EXCHANGE?
15                                 DR,  COLBY:  IF I DIG IN MY
16       BRIEFCASE FOR  A  MINUTE,  IN A BASIC SOLUTION?
17                                 up QJ\£V$.    NO, JUST A NEUTRAL
18        SOLUTION,
19                                 DR,  COLBY:  IN A NEUTRAL
20       SOLUTION, IF YOU  DO IT VERY, VERY RAPIDLY, SPIKE   IN
21       YOUR SYRINGE,  PUT THE VOA SAMPLE IN, AND PURGE  IT,
22       YOU'RE  ONLY TALKING IN  THE 10 PERCENT AREA,  IT'S VERY
23       REPRODUCIBLE,   WE'VE DONE  ISOTOPE DILUTION WITH
24       DEUTERATED  CHLOROFORM AND WE GET VERY REPRODUCIBLE
25       AND ACCURATE RESULTS, BUT  I WOULD HESITATE TO USE  IT
                                  90

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 1       ON A ROUTINE BASIS BASED ON THE FACT THAT  I  KNOW  IT
 2       DOES EXCHANGE,  IF THE SAMPLE  IS BASIC, THE
 3       EXCHANGE IS 100 PERCENT AND IT'S FAST,  It's VERlY
 4       PH DEPENDENT,
 5                                MR. CUFYS: RIGHT,
 e                                MR, PARR:  JERRY  PARR WITH
 7       RADIAN,  CORRECT ME IF I'M WRONG,, BUT  I GET  THE
 8       IMPRESSION ON YOUR COST FACTORS THAT YOU WERE GOING
 9       TO BE ABLE TO USE ALL OF THE'DEUTERATED MATERIAL
10       WHEN IN ACTUAL LAB PRACTICE, THE BASIS OF  WASTAGE
11       AND THE STABILITY OF THE STANDARDS AND HAVING TO
12       REMAKE THEM, THAT COULD BE ONLY MAYBE 10 PERCENT
13       OF WHAT YOU USE, WHICH WOULD MULTIPLE YOUR  COSTS BY
14       A FACTOR OF 10, WHICH BECOMES SIGNIFICANT,  THEN, IN
15       AN ANALYTICAL SITUATION.
is                                DR, COLBY:  I DON'T THINK I
17       FOLLOWED THAT,
18                                MR, PARR:  YOUR COST PER
19       YOUR STANDARD IN WHICH YOU CAME UP WITH $5,
20                                DR, COLBY:  COST  PER SAMPLE,
21       RIGHT,
22                                MR, PARR:   IF YOU BUY A  GRAM
23       OF THAT, HOW MUCH OF THAT GRAM ARE YOU GOING TO BE ABLE
24       TO USE FOR SPIKING?
25                                DR, COLBY:  THAT  MAKES THE

-------
1        ASSUMPTION THAT WE'RE GOING TO USE THE WHOLE GRAM UP
2        OVER SOME PERIOD OF TIME AND WE'RE NEVER GOING TO
3        WASTE ANY OF IT,
4                                 MR, PARR:  YES, AND I'M SAYING
5       I THINK YOU'RE GOING TO WASTE 50 TO 80 PERCENT OF THAT
6       GRAM IN TERMS OF HAVING TO REMAKE YOUR STANDARDS OR THE
7       STABILITY OF YOUR STANDARDS OR THE FACT THAT YOU'VE
8       GOT,,,
9                                DR.-COLBY:  So IT MAY COST...
10                                MR, PARR:  $50,
11                                DR, COLBY:  REALLY?  No, YOU'RE
12       WASTING ALMOST 1,000 PERCENT,  IF YOU WASTE 50 PERCENT
13       FOR EVERY 100 MICROGRAMS NEEDED IN PRACTICE YOU
14       ACTUALLY WASTE 100, SO YOU'D CONSUME 200; THAT WOULD
15       MAKE IT $10,
16                                MR, TFLLIARD:  You COULD WASTE
17       $50 AT THE PRICE YOU GUYS ARE CHARGING US FOR SAMPLES,
18       IT'S WSTGNIFICANT,       I'M NOT SINGLING YOU OUT, I
19       MEAN THESE GUYS,
20                                MR, PARR:  BUT IT GETS  INTO
21       EACH TIME YOU NEED TO MAKE,,,IT'S NOT ONLY THE COST OF
22       THE MATERIAL, BUT THE COST OF THE LABOR AND PREPARING
23       FRESH STANDARDS OVER THE PERIOD AND WHATEVER; I THINK
24       IT CAN EVENTUALLY BECOME A FACTOR,
25
                                  .22.

-------
 ,                                 DR, COLBY:  YOU'RE  NOT  ADDING
 2      TO THE  SITUATION. YOU'RE JUST SAYING THAT IT'S THE  SAME  WITH THE
 3       ISOTOPICALLY LABELED  COMPOUNDS,   YOU HAVE TO  MAKE UP
 4       ALL THOSE SOLUTIONS NOW  JUST AS YOU WOULD WITH THE
 5       LABELED COMPOUNDS; THERE'S NO DIFFERENCE,
 6                                 MR, PARR:   YES, BUT SPIKING
 7       1 IN 10 VERSUS SPIKING EVERY SAMPLE,
 8                                 DR, COLBY:  ALL RIGHT, YES,
 9       IF YOU WANT TO SPIKE  1 IN 10,
10                                 MR, PARR:   YES,  OKAY, THAT'S
11       ALL,
12                                 MR, STANKO:  GEORGE STANKO,
13       SHELL DEVELOPMENT,  I'D  LIKE TO SUGGEST ONE  FURTHER
14       EXPERIMENT ON THIS SPIKING THAT I  THINK IS IMPORTANT,
15       I WOULD LIKE TO  SEE YOU  TAKE A LIQUID/LIQUID EXTRACTABLE
16       SAMPLE AND FIELD SPIKE IT AT THE  TIME THE SAMPLE WAS
17       OBTAINED, TRANSPORT THE  SAMPLE BACK TO THE LABORATORY,
18       THEN ANALYZE THAT PARTICULAR SAMPLE,  THEN, TAKE THE
19       SPLIT OR EQUIVALENT SAMPLE THAT WAS OBTAINED IN THE
20       FIELD, COLLECT IT AT  THE LAB,  PUT IT IN YOUR CONTINUOUS
21       EXTRACTOR AND THEN SPIKE WITH YOUR  STABLE LABEL,   I
22       THINK  IF YOU CAN DEMONSTRATE THAT THERE IS NO DIFFERENCE
23       WHICH  I THINK THERE WILL BE, I THINK THIS IS AN
24       IMPORTANT THING  TO CONSIDER,
25                                 DR, COLBY:   RIGHT,  WE'VE  JUST
                                 93

-------
1       CONSIDERED WHAT HAPPENS AFTER THE SAMPLES  ARRIVE IN
2       OUR LABORATORY AND HAVE NOT CONSIDERED  ANYTHING THAT
3       MIGHT GO ON IN TRANSIT OR  IN THE FIELD,
4                                FIR, STANKO:  THAT'S  AS
5       IMPORTANT AS ANALYZING IT,
e                                DR, COLBY:   I  AGREE.
7                                MR, DAl'N:  BOB DAUN,  RALTECH
s       SCIENTIFIC.  IN YOUR REVERSE EXCHANGE EXPERIMENTS.,
9       WHERE YOU EQUILIBRATED THE PRIORITY POLLUTANTS, I
10       ASSUME YOU USED DEUTERATED WATER?
11                                DR, COLBY:   WE USED ly], AND
12       USED DCL  AND NAOD TO ADJUST THE  PH,
13                                MR, DAUN:  WHAT  RELATIVE
14       CONCENTRATIONS OF PRIORITY POLLUTANT  TO THE  DEUTERATED
15       WATER WERE USED?  IN OTHER WORDS, DID YOU USE, SAY,
is       YOU DIDN'T USE 100 PERCENT DEUTERATED WATER  OR
17       DEUTERATED,,,
is                                DR, COLBY:   100  PERCENT,
19                                MR, DAUN:  IT  WAS 100  PERCENT?
20        '                        DR, COLBY: WELL,  THAT'S WHAT
21       THE MANUFACTURER TOLD ME,
22                                MR, DAUN:  YES,   OKAY,  I  WAS
23       WONDERING  IF IT WAS, YOU KNOW, SOMETHING  DOWN  IN A VERY
24       LOW RANGE OR IF IT WAS SOMETHING HIGH THAT WOULD
25       REPRESENT A REAL SAMPLE-TYPE THING,   THANK YOU,
                                 _94.

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1
2
3                                MR, SPRAGGINS:   BOB SPRAGGINS,
4       RADIAN CORPORATION,  YOUR PRICE  PER  SAMPLE,  THAT'S
5       BASED ON, LET'S SAY IF YQU'RE GOING TO  DO  BENZENE IN
6       WATER, YOU'RE ADDING D£  BENZENE,  IS  THAT  CORRECT?  IF
7       YOU WERE GOING TO DO 10 COMPOUNDS  IN WATER YOU WOULD
8       ADD 10 INTERNAL STANDARDS SO THAT  YOUR PRICE PER SAMPLE
9       WOULD BE 10 TIMES THAT AMOUNT, CORRECT?
10                                DR, COLBY:  RIGHT AND THE
11       PRICE PER SAMPLE THAT I HAD  IN THE SLIDE  WAS BASED ON,,,
12                                FIR, SPRAGGINS:   ISN'T THE
13       REAL PROBLEM IN,., IS THAT IF YOU'RE  DOING 10 OR 40
14       PRIORITY POLLUTANTS AND YOU ADD  10 TO  40  SPIKES, YOUR
15       SPECTRUM GETS SO CLUTTERED THAT  YOU  HAVE  A REAL
16       POSSIBILITY OF INTERFERENCES,1  ISN'T  THAT  THE REAL
17       PROBLEM?
18                                DR, COLBY:   I DON'T REALLY
19       THINK THAT WE'RE TALKING ABOUT  INTERFERENCES,  l'/E LIKE
20       THIS METHOD BECAUSE WE ARE MAKING  THE  MEASUREMENT
21       FOR LABELED AND UNLABELED MATERIAL AT  THE SAME INSTANT
22       IN THE ION SOURCE  IN MOST CASES,   IF THERE ARE ANY
23       FLUCTUATI-ONS IN INSTRUMENT PERFORMANCE,  THOSE  WOULD BE
24       CANCELLED OUT,  THE OBJECT  IS  TO CANCEL OUT AS MUCH  AS
25       WE CAN,  YES, THERE WILL BE  INTERFERENCES OCCASIONALLY,
                                 95

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                                  MR,  SPRAGGINS:   MY ONLY POINT
2       is, IN  A  MASS  SPECTRUM,  THERE'S USUALLY MORE THAN TWO IONS,
3       FOR EACH COMPOUND  IT'S  GOING  TO GENERATE ITS   OWN,,,
4                                 DR,  COLBY:  THAT'S RIGHT,
5                                 MR,  SPRAGGINS:   ,,,so YOU'RE
6       GOING  TO HAVE A  LOT  MORE  POSSIBILITY FOR INTERFERENCE
7       THE MORE THINGS  THAT YOU  SHOVE IN THERE,
8                                 DR,  COLBY:   IF  YOU CHECK BACK
9       INTO  NASS  SPEC  IN  TERMS OF THE SPECTRA AND THE WAY THEY
10       LOOK,  USUALLY WE SEE LOSSES OF CERTAIN NUMBERS OF
11       MASS UNITS  BEFORE  ANOTHER GROUP OF PEAKS, AND WHEN
12       WE'RE  LABELING  COMPOUNDS, WE  ARE NOT TALKING ABOUT
13       LABELING THEM SUCH THAT WE WOULD  HAVE A METHYL GROUP
14       AND LABEL  IT  WITH  15 DEUTERIAj THAT WOULD GUARANTEE US
15       OVERLAPS AND  THINGS  LIKE  THAT,
16                                 MR,  SPRAGGINS:   As I SAY, I
17       AGREE  THAT  YOUR  METHOD  IS BETTER THAN WHAT WE'RE USING;
18       I'M JUST SAYING  THAT THERE ARE PRACTICAL LIMITATIONS
19       TO IT.
20                                 DR,  COLBY:   RIGHT,
21
22
23
24
25
                                    96

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                                 MR, TELLIARD:  THANK  YOU,
2       BRUCE.   IN PASSING, LET ME POINT OUT THAT BRUCE  is
3       GOING TO CONTINUE ON THE WORK AND HE'S BEEN  FUNDED
4       BY LARRY JOHNSON FROM RTP TO PURCHASE THE COMPOUNDS,
5       HAVE COMPOUNDS MADE.  IN ADDITION TO THAT, THE FOLKS
e       AT CINCINNATI HAVE AGREED TO LOOK AT ADDITIONAL
7       COMPOUNDS BEING SYNTHESIZED OVER THE NEXT MONTHS
8       OR WHATEVER AS THEY LOOK AT WHAT THEY FEEL MIGHT BE
9       NEEDED,   HOPEFULLY, IN A COUPLE OF MONTHS WE WILL
10       HAVE A LOT MORE  DATA  ON REAL SAMPLES,  THERE WILL
        BE TWO OTHER LABS PARTICIPATING IN IT, RUNNING REAL
12       SAMPLES, SO TO SPEAK.
13                                AFTERNOON SESSION
14                                MR, TELLIARD:  OUR  NEXT
15       SPEAKER is BOB KLEOBFER FROM OUR REGION 7 S&A  LABORATORY,
16       BOB HAS APPEARED HERE BEFORE AND WE'LL KEEP  MAKING HIM
17       DO  IT UNTIL HE GETS IT RIGHT,  WE PASSED OUT COPIES OF
18       A PAPER BOB HAS PUT TOGETHER ON A REVIEW OF  THE
19       QUALITY ASSURANCE FOR PRIORITY POLLUTANT ANALYSIS THAT
20       HE HAS WRITTEN AND  OB IS GOING TO BASICALLY GO OVER
21       THE PAPER TODAY AND KIND OF SUMMARIZE WHAT IT  CONTAINED,
22
23
24
25
                                 96

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                     PRIORITY POLLUTANT METHODOLOGY

                   QUALITY ASSURANCE REVIEW, REGION VII

 1

 2                        BY:ROBERT D,KLEOBFER


          THIS  IS THE  FOURTH  CONFERENCE THAT HAS  BEEN  HELD
 O

 4       ON THE  PRIORITY  POLLUTANT METHODOLOGY,  AND UNFORTUNATELY/


        OR MAYBE FORTUNATELY, DEPENDING ON  YOUR POINT OF
 O

        VIEW, I HAVE ATTENDED ALL FOUR,   I  HAVE COME UP  WITH
 6

        ONE OBSERVATION  ABOUT ANALYTICAL  CHEMISTS,   I  SUSPECT


        THAT  IF YOU WERE TO CLONE  AN ANALYTICAL CHEMIST,  AND
 8

        YOU WOULD HOLD A MEETING LIKE THIS  WITH ALL OF HIS
 9

        CLONES;  I SUSPECT THERE  WOULD STILL  BE  DISAGREEMENT
10

        ABOUT METHODOLOGY AMONG THE  CLONES,  IN SPITE  OF THOSE
11

        PROBLEMS WITH  ANALYTICAL CHEMISTS,  I THINK THE BASIC
12

        SCREENING PROTOCOL THAT WAS  PROPOSED TWO  OR THREE
13

        YEARS AGO DID  TURN OUT  AND HAS BEEN DEMONSTRATED TO
14

        BE A  SOUND ONE,  OVER THE PAST FEW  MONTHS I HAVE
15

        ATTEMPTED TO ACCUMULATE AS MUCH DATA AS I COULD  FROM
16

        VARIOUS CONTRACTORS  AND VARIOUS LABORATORIES ABOUT


        THE QUALITY OF THE DATA THAT HAS  BEEN  GENERATED
18

        USING THAT BASIC METHODOLOGY AS THE GUIDELINE,
19

        THIS  PAPER THAT  WE HAVE PASSED OUT  IS  BASED ON THE
20

        RESULTS FROM SEVEN DIFFERENT LABORATORIES AND  IT
21

        INCLUDES OVER  10,000  DATA POINTS,   So  THERE  IS QUITE
22

        A BIT OF  INFORMATION  AVAILABLE  NOW ON RECOVERY OF
23

        STANDARDS TO EITHER  BLANK WATER OR  TO  REAL SAMPLES,
24

        THIS  PAPER SIMPLY ATTEMPTS TO SUMMARIZE DATA
25
                                 97

-------
 1        THAT  WAS  AVAILABLE  TO  ME.   SEVEN LABORATORIES



 2        SUPPLIED  THE  DATA,   I  SUPPOSE I  SHOULD START RIGHT



 3        OUT AND  IMPLICATE,  OR  ACKNOWLEDGE,  RATHER THAN



 4        IMPLICATE,  THE  LABORATORIES THAT SUPPLIED DATA,



 5        THE PRIMARY ONES  WERE  VERSAR, CARBORUNDUM, AND



 e        A,D,  LITTLE AND  THE REGION  VII LAB,



 7           I WILL START  RIGHT OFF  AND JUST  GIVE THE BOTTOM



 8        LINE  AS  FAR AS THE  ORGANICS GO,  HOW  WELL WE DID ON



 9        RECOVERING STANDARDS WHICH  HAVE  BEEN ADDED TO



10        SAMPLES,  WHAT  I  DID is SIMPLY AVERAGE THE RECOVERIES



'n        FOR ALL  OF THE ORGANICS,  THIS IS SIMPLY LUMPING



12        A  LOT OF  DATA TOGETHER AND  THE RESULT WAS 73 PERCENT



13        RECOVERY  WITH A  STANDARD DEVIATION BEING 26 PERCENT,



14        I  THINK  THIS  IS  WHAT HAD SURPRISED MOST OF US FROM



15        THE BEGINNING; WE DID  NOT THINK  THAT WE COULD DO



16        THAT  WELL, BUT THIS IS WHAT WE CAME  UP WITH,



17           NOW,  I HAVE  BASICALLY ASSEMBLED  THE DATA INTO



18        EIGHT DIFFERENT  TABLES AND  RATHER THAN TRYING TO PUT



19        IT ON A  SLIDE PROJECTOR OR  THE OVERHEAD PROJECTOR,



20        IT WOULD  BE MORE  CONVENIENT TO SIMPLY REFER TO THE



21        PAPER THAT I  HANDED OUT,



22           LET'S BEGIN  WITH TABLE  NUMBER ONE, WHICH BEGINS



23        AT THE END OF ALL OF THE DIALOGUE,   TABLE NUMBER



24        ONE,  THAT SHOULD  READ   INTERLABORATORY COMPARISON,



25        RATHER THAN   INTRALABORATORY,  IT GIVES COMPARISON
                                   98

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                  TABLE I.  INTRALABORATORY COMPARISON3
Priority
Pollutant
Fractionb
Volatile
(MS)
Volatile
Sample Spike
Acid (MS)
Acid Sample
Blank
B/N-(MS)
B/N Sample
Spike
Pesticide
(MS)
LAB
I
88+21
82^24
90+_18
92+34
95+25
84^18
73^8
LAB
II
95+_5
10H9
89^5
72+10
78+41
61+22
74+19
LAB
III
_
93^13
-
62^12
-
55+24
-
LAB LAB LAB
IV V VII
100+8 -
107+9 -
67+_14 82^16 -
60^15 84^17 -
77+_15 -
68^16 - 63^13
88+8
Averagec
90^13
92+15
84^13
76^19
84^25
68+^21
78+11
Pesticide
Sample Spike
69+7
51+18   33+10    93+5
Metals (MS)
Metals
Sample Spike
Cyanide (MS)
Cyanide
Sample Spike
Phenol ics
(MS)
Phenol ics
113^37
100+20
103^14
10U12
10^13
93+15
-
103^14
-
-
97+_6
98+10
103+^8 -
92+_7
103+8 -
93^16 -
100^7 -
97+9
108+_22
96^11
103^7
96^14
10H8
96+11
Sample Spike

a)  The values are in units of percent recovery (P) plus or minus (+) one
standard deviations (Sp).
b)  MS refers to the method standard or the standard addition to blank water.
Sample spike refers to the standard addition to a sample.
c)  P and Sp are weighted averages based on the number of data points
contributed by each laboratory.

                                        98A

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 1        OF  DATA  SUPPLIED  BY  THE  DIFFERENT LABORATORIES,
 2        BROKEN DOWN  THIS  TIME  BY THE VARIOUS FRACTION TYPES,
 3        THE FIRST  ENTRY BEING  THE VOLATILES WITH THE
 4        STANDARD HAVING BEEN ADDED TO A BLANK SAMPLE;
 5        THE SECOND ENTRY  BEING THE VOLATILE RESULTS WITH
 6        THE SPIKE  BEING ADDED  TO AN ACTUAL SAMPLE,   YOU CAN
 7        SEE THAT THERE  IS A  REASONABLE AGREEMENT BETWEEN
 8        THE DIFFERENT LABORATORIES,   THEN,  IF YOU SCAN DOWN
 9        THE LAST COLUMN,  WHICH SIMPLY AVERAGES EVERYTHING
10        TOGETHER,  YOU CAN SEE  THAT IN ALL CASES EXCEPT FOR
n        THE VOLATILE FRACTION, THE RECOVERY FROM THE SAMPLES,
12        THE REAL SAMPLES,  WERE LESS THAN  THE RECOVERY WHEN
13        STANDARDS  WERE ADDED TO  A BLANK WATER SAMPLE,   FOR
14        THE VOLATILES, WE SEEMED TO DO WELL WHETHER IT WAS
15        A SAMPLE OR  A BLANK  WATER MATRIX.
16            NOW, ONE INTERESTING THING I  WOULD LIKE TO
17        POINT OUT  HERE  IS THAT WE STARTED OUT WITH
18        METHODOLOGY  THAT  WAS SUBSTANTIALLY  UNPROVEN EXCEPT
19        FOR THE  PESTICIDES,  THE PESTICIDE  METHODOLOGY WAS
20        THE STANDARD GC ELECTRON CAPTURE  METHOD, AND YOU
21        CAN SEE  THAT, OUT OF ALL THE  FRACTIONS,  THAT THE
22        PESTICIDES GAVE US THE LOWEST RECOVERY,   So HERE
23        WAS AN ESTABLISHED METHOD THAT GIVES US LOWER
24        RECOVERY THAN THE OTHER  METHODS,
25
                                   99

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 1           NOW.,  IF  WE  GO  ON  TO TABLE TWO,  WE BEGIN TO LOOK




 2       AT THE  SPECIFIC COMPOUNDS  IN THE VARIOUS GROUPS,




 3       AND AGAIN  THE RESULTS FROM ALL OF THE LABORATORIES




 4       HAVE BEEN  LUMPED TOGETHER, AND WE COME OUT




 5       WITH SORT  OF AN AVERAGE STATEMENT ON THE PRECISION




 6       AND ACCURACY THAT  WERE OBTAINED FROM THESE SEVEN




 7       DIFFERENT  LABORATORIES,   ON THE VOLATILE FRACTION




 8       WHICH  IS COVERED IN TABLE  TWO,  WE DO NOT SEE ANY




 9       REAL SURPRISES,  THERE DID SEEM TO  BE SOME PROBLEM




10       WITH DICHLOROMETHANE,  AND  I CANNOT  IMAGINE WHY WE



11       WOULD  HAVE PROBLEMS WITH DICHLOROMETHANE,   BUT,




12       SERIOUSLY, IN OUR  OWN LABORATORY THE BLANKS, ON




13       OUR OWN PREPARED WATER,  TYPICALLY CONTAINS 1 TO 2




14       PARTS  PER  BILLION  OF  METHYLENE CHLORIDE; IT IS A




15       PROBLEM THAT IS HARD  TO DEAL WITH,  HARD TO SOLVE,




16           THE DATA, BY THE  WAY,  THAT IS LUMPED TOGETHER




17       IN TABLE TWO GENERALLY IS  IN THE RANGE OF 10 TO




18       1,000  PARTS  PER BILLION WITH MOST OF THE DATA IN




19       THE 20  TO  200 CATEGORY,   WE CHOSE NOT,  AT THIS



20       POINT,  TO  TRY TO SEPARATE  INTO LOW  LEVEL SPIKES AND




21       HIGH LEVEL SPIKES  BECAUSE  ON JUST SCANNING THE DATA



22       WE DID  NOT SEE  ANY REAL SIGNIFICANT DIFFERENCE IN




23       LOW LEVEL  COMPARED TO HIGH LEVEL.




24



25
                                  100

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                        TABLE II.  Purgeable Organics3
Compound
Acrolein
Acrylonitrile
Benzene
Bromodi chloromethane
Bromoform
Bromomethane
Carbon Tetrachloride
Chlorobenzene
Chlorodibromomethane
Chloroethane
Chloroform
Chloromethane
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethylene
trans-1,2-Dichloroethylene
Di chl oromethane y^
1,2-Dichloropropane
cis-1,3-Dichloropropene
trans  -1-3-Dichloropropene
Ethyl benzene
Methodb
Standard
77+30
96+31
89+12
97+11
94+J4
90+16
91+_23
94+23
86+12
67+22
90+18
91+22
108+11*
83^10
102^12
74+_24
90+25
82+46
94+26
95+15
91+13
109+19
Standard0
Spike
32+30
102+_28
93+24
103+_31
88+12
78+15
91+33
103+24
99+17
60+_23
91+_26
64+^28
114+_8*
87+_21
103+27
80+32
85+_35
66+66
99+_30
98+_20
93+16
106+28
                                      100A

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                         Continuation of Table II
                                       Method                    Sample
Compound                               Standard                  Spike
1,1,2,2-Tetrachloroethane               8H31                     784-31
Tetrachloroethylene                     97+13                     99+_26
To! uene                                 96+_22                     97+_25
1,1,1-Trichloroethane                   92^21                     94+36
1,1,2-Trichloroethane                  102^14                     103^19
Trichloroethylene                      106+14                     110^22
Trichlorofluoromethane                  59+_23                     67+48
Vinyl Chloride                         103+30                     79+22
 a) The values  are  in terms of P _+ Sp.  Data from 2-4 laboratories have been
 averaged  except where noted with an (*) asterik.  In general the concentration
 added ranged from  10 to 1000 parts per billion.
 b) Standard addition to blank water-
 c) Standard addition to sample.
 *Data from only one lab were available.
                                   100B

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 1            NOW,  I  AM  SURE  THAT  THE RECOVERIES AND THE
 2        STANDARD  DEVIATION  ARE GOING TO BE WORSE IF WE
 3        WERE TO LOOK AT  LEVELS,  SAY, BELOW 10 PARTS PER
 4        BILLION,  WHERE WE ARE  REALLY CHALLENGING THE
 5        ANALYTICAL  METHOD,
 e            TABLE THREE  SUMMARIZES  THE DATA FOR THE ACID
 7        FRACTION, THE  PHENOLICS,  THERE ARE NOT ANY REAL
 8        SURPRISES HERE,  EXCEPT PERHAPS THERE WAS MENTION
 9        EARLIER THAT PHENOL IS GENERALLY RECOVERED AT 40
10        TO  50 PERCENT,
n            TABLE FOUR SUMMARIZES THE BASE NEUTRAL DATA AND
12        HERE WE DO  ENCOUNTER SOME PROBLEM COMPOUNDS,
13        COMPOUNDS THAT WE CANNOT DO AS WELL AS OTHERS, AND
14        ONE,  FOR  EXAMPLE, WOULD  BE  THE PHTHALATE ESTERS,
is        GENERALLY THE  RECOVERIES ARE QUITE LOW AND THE
16        SCATTER IS  A LOT WORSE.
17            OF COURSE, WE ALL  KNOW  THAT DICHLOROBENZIDINE
18        IS  SOMEWHAT DIFFICULT  TO DO, AND THAT IS WHY YOU
19        HAVE SUCH A LARGE STANDARD  DEVIATION ON THAT ONE,
20        I SUSPECT,  THE  HEXACHLOROCYCLOPENTADIENE RECOVERIES
21        ARE NOT ANYTHING TO BRAG ABOUT,  AND HERE WE
22        SUSPECT THERMAL  DEGRADATION AT THE INJECTOR IS
23        COMING INTO PLAY HERE,
24
25
                                 JLQ1

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COMPOUND
2-Chlorophenol
4-Chloro-3-methylphenol
2,4-Dichlorophenol
2,4-Dimethyl phenol
4,6-Dinitro-£-cresol
2,4-Dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorphenol
Phenol
2,4,6-Trichlorphneol   "*
TABLE III.  ACID FRACTION*
       METHODb
       STANDARD
       80+22
       96+16
       86+24
       71+19
       87+_34
       89+22
       95+22
       65+33
       87+_24
       6H11
       91+22
SAMPLES
 SPIKE
  71+23
  99+19
  84+23
  72+16
 102+23
  92+40
  87+22
  59+46
  84^22
  54+24
  80+24
a)  The values are in terms of P +^ Sp.  Data from 2-5 laboratories have
been averaged.   In general the concentation added ranged from 20 to 2500
parts per billion.
b)  Standard addition to blank water.
c)  Standard addition to sample.
                                     101A

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                       TABLE IV  BASE/NEUTRAL FRACTIONA
Compound
Acenaphthene
Acenapthylene
Anthracene^
Benzidine
Benzo(a)anthracenee
Benzo(b)f1uoranthenef
Benzo(k)fluoranthenef
Benzo(a)pyrene
Benzyl Butyl Phthalate
Bis(2-chloroethyl) Ether
Bis(2-chlorofsopropyl) Ether
Bis(2-ethylhexyl) Phthalate
4-Bromophenyl Phenyl Ether
2-Chloronaphthalene
Chrysene6
Dibenzo(a,h)anthracene
Di-n-butyl Phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
Method^
Standard
90_+22
83+22
98+20
44+27
105+33
96+68*
96+68
90^22
49+39
98+48
154^136
70+33
80+25
88+20
105+33
80+42
80+32
65+24
67+21
67+22
71+85
Sampl ec
Spike
78+24
79+27
79+26
40+29
51+24
41+21
47+27
43+21
49+22
80+49
96+88
66+50
63+25
79+21
77+27
36+_29
58+27
65+27
62+20
63+21
62+45
                                       101B

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Compound
Diethyl Phthalate
Dimethyl Phthalate
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Di-n-octyl Phthalate
1,2-Diphenylhydrazine
(and/or Azobenzene)
Fluoranthene
Fluorene
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadi ene
Hexachloroethane
Isophorone
Indeno(l,2,3-cd)pyrene
Naphthalene
Nitrobenzene
N-ni trosodi pheylami ne
(and/or Diphenylamine)

N-Ni trosodi -^-propylamine
Phenanthrene
Pyrene
1,2,4-Trichlorobenzene
Methodb
Standard
7U37
43+_37
122^55
115+41
84+44
97+26
111+26
98^24
98+^31
76+26
38+28
63+22
66+_36
109+14
83+24
106+31
72+22
86+34
98+20
Sample0
Spike
65+37
66+43
94^45
104+35
88+32
91+32
63+20
88+_25
76+_31
77+45
27+10
58+23
67+_22
40^21
89+51
77^51
66+^25
71+22
79+20
142+41
74+22
63+20
69+24
 a)  The  values  are  in terms of P ^ Sp.  Data from 2-5 laboratories have been
 averaged except where noted with an  (*) asterik.  In general the concentration
 added  ranged from 10 to 500 parts per billion.
 b)  Standard addition to blank water.
 c)  Standard addition to sample.
 d,e,f) These isorner? pairs are not separted by packed column GC.  Also mass specti
 data are not sufficiently unique to  allow differentiation.
 *Data  from only one lab were available.
                                     101C

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 i            THEN.  WE MOVE  ON  TO  TABLE  FIVE,   WE HAVE GOT
 2        THE  PESTICIDE  DATA SUMMARIZED,   THE  ONE COMPOUND
 3        THAT STANDS OUT  IS.  ENDRIN  ALDEHYDE.  WITH A LARGE
 4        SCATTER  ON THAT  DATA,  HERE WE  SUSPECT THAT THE
 5        MATERIAL IS SIMPLY SENSITIVE TO OXIDATION,   THE
 6        LEVELS OF  SPIKING  FOR  THE PESTICIDES.  BY THE WAY.
 7        ARE  QUITE  A BIT  LOWER  THAN  FOR  THE OTHER FRACTIONS,
 8        FOR  THE  PESTICIDES THE SPIKING  CONCENTRATION RANGED
 9        IN GENERAL FROM  A  TENTH  OF  A PART PER BILLION UP
10        TO 100 PARTS PER BILLION,   So THIS.  IN PART. COULD
11        EXPLAIN  THE SOMEWHAT  LOWER  RECOVERIES FOR THE
12        PESTICIDE  FRACTION,
13            THEN IF WE MOVE  ON TO TABLE six.  WHICH  COVERS
14        THE  METALS. CYANIDE.  AND PHENOLICS BY THE
15        COLORIMETR1C TEST.  WE  HAVE  GOT  A LOT  OF DATA
16        SUMMARIZED THERE,   I DO  NOT THINK THERE ARE ANY
17        REAL SURPRISES THERE.  OUR  LABORATORY HAS JUST
18        COMPLETED  A COMPARABILITY STUDY WHERE WE ACTUALLY
19        COMPARED ATOMIC  ABSORPTION  METHODOLOGY DIRECTLY
20        WITH ICP METHODOLOGY.  INDUCTIVELY COUPLED PLASMA.
21        AND  WE DO  HAVE A PAPER AVAILABLE ON THAT RIGHT
22        NOW  AND  IT SUMMARIZES  OVER  5.000 DATA POINTS,
23            I DID  NOT  BRING  120  COPIES  WITH ME BECAUSE
24        IT IS A  MUCH LARGER  DOCUMENT. BUT IF  YOU DO CARE
25
                                 L02

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                      TABLE V.   PESTICIDE FRACTIONS
Methodb
Standard
72+13
78+13
79+21
78+;! 4
82+16
81+17*
82^14
76+14
85+17
71+14
65+14
67+19
74+39*
82+25
64+76*
72+12
82^14
83+11*
89+12*
Sampl ec
Spike
55+12
55±12
57+22
64+11
61+16
39+9*
62^16
57+18
76+_26
62^16
61+13
66+14
84^30*
68+18
34+39*
49+12
65+11
42^13
.
Compound
Aldrin
alpha-BHC
beta-BHC
gamma-6HC
delta-BHC
Chlordane
4,4'-ODD
4,4'-DDE
4,4'-DDT
Dieldrin
Endosulfan I
Endosulfan II
Endosulfane Sulfate
Endrin
Endrin Aldehyde
Heptachlor
Heptachlor Epoxide
PCB
Toxaphene
a)  The values are in terms of P _+ Sp.  Data  from 2-4 laboratories have been
averaged except where noted with an  (*)asterik.   In general  the concentration
added ranged from 0.1 to 100 parts per billion.
b)  Standard addition to blank water.
c)  Standard addition to sample.
*Data from only one lab were available.
                                      102A

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PARAMETER
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury^
Nickel
Selenium
Silver
Thallium
Zinc
Cyanide
Total Phenols
TABLE VI.  METALS, CYANDIE,  AND PHENOLICSa
                 METHOD^
                 STANDARD
                     61+_47*
                   120+20
                     89+16
                     91+18
                     99+30
                   136+70
                   116+32
                     83+_24
                     84+_62
                   112115
                   110+25
                     99+33*
                   122+44
                   103±7
                   101+8
SAMPLES
 SPIKE
  103+24
   97+25
   94+_20
   98+_23
  106+25
   99+24
   93+25
   79+38
  101+26
   93+20
   80+25
   95+23
   106+37
   96+14
   96+11
a)  The values are  in terms  of P  +_ Sp.   Data from 2-3 laboratories have been
averaged exept where noted with an (*)  asterik.  In genral the concentration
added ranged from 10 to  1000 parts per  billion.
b)  Standard addition to blank water.
c)  Standard addition to sample.
d)  Analyzed by the cold vapor technique.
*Data from only one lab  were available.
                                     102B

-------
 1       TO SEE THAT DOCUMENT, JUST  LEAVE ME  YOUR  NAME  AND



 2       MAILING ADDRESS AND  I WILL  SEE THAT  YOU GET  ONE,



 3           THE BOTTOM LINE  ON THAT STUDY  IS SIMPLY  THAT



 4       THE TWO METHODS ARE  INDEED  COMPARABLE,  THERE  ARE



 5       SOME METALS THAT ARE BIASED HIGH ON  ICPj  OTHER



 6       METALS ARE BIASED  SOMEWHAT  HIGH ON AA, BUT  IN



 7       GENERAL THE RESULTS  ARE  QUITE COMPARABLE,



 8           IF WE MOVE ON  NOW TO TABLL SEVEN, HERE WE  HAVE



 9       SUMMARIZED THE DATA  AT LEAST THAT  I  HAD AVAILABLE



 10       ON SURROGATE  RECOVERIES, AND THESE ARE COMPOUNDS,



'n       OF COURSE, THAT ARE  ADDED TO THE SAMPLE BEFORE THE



 12       EXTRACTION OR THE  SPARGING  IN THE  CASE OF THE



 13       VOLATILES,  THERE  is SOMEWHAT MORE LIMITED DATA



 14       AVAILABLE ON  THE SURROGATES, BUT THE RESULTS



 15       ARE SUMMARIZED HERE  AND  I THINK YOU  CAN READILY



 16       SEE THAT THERE ARE SOME  COMPOUNDS  WHICH ARE  NOT



 17       GOOD CHOICES  AS SURROGATES, ONE SUCH BEING THE



 18       DEUTERATED CHLOROFORM WHICH WAS DISCUSSED A  WHILE



 19       AGO AS BEING  A PROBLEM WITH THE DEUTERIUM EXCHANGE,



 20           YOU CAN SEE THE  DATA FOR THAT  PARTICULAR COMPOUND



 21       HAS A GREAT DEAL OF  SCATTER TO  IT, AND  IF YOU



 22       COMPARE THAT  WITH  WHAT WE GET ON THE SCATTER FROM



 23       THE NONDEUTERATED  CHLOROFORM,  IT SIMPLY  IS NOT A



 24       GOOD SURROGATE.  ON  NONDEUTERATED  CHLOROFORM THE



 25
                                  103

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                TABLE VII.  PRIORITY POLLUTANT SURROGATES*
Compound                   LAB IIIb
(Purgeable Orgnaics)
ds-Benzene
Bromochloromethane
d-Chloroform               139+96
1,4-Dichlorobutane
d4-l,2-Dichloroethane      119.+29
d2-Dichloromethane         146+55
dio-Ethylbenzene           102+25
Fl uorbenzene               96+_20
dg-Toluene
ds-1,1,1-Trichloroethane   117+_41
(Acids)
2-Fluorphenol               76+36
Pentafluorphenol            84+_30
d5-Phenol                   55+20
Trifluoro-m-cresol         72^42
(Base/Neutral)
Decaf luorobiphenyl          39+^18
ds-Nepthalene               76+22
2-fluornaphthelene          75+20
1-fluronaphthelene          69+^18
di2-benzo(a)anthracene      68+16
2-flurobiphenyl             63+5
                            57+36
LAB
 93+22
 91+20

 85+24
LAB Vllld
 94+18
 92+18
 50+22
  41+29
 101+39
  46+13
                                     103 A

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Table  VII  (cont'd)

Compound            LAB IIIb              LAB IVC               LAB VI I
2-fluroaniline       74+39

ds-nitrobenzene      70+21


a)  The values are in terms of P _+ Sp.  The concentration added ranged from
20 to 200 parts per billion.
b)  The matrix for these surrogates included influent and effluent samples
from 12 different industrial categories.
c)  The matrix for these surrogates included POTW, detergent, and chemical
disposal industries.
d)  The matrix for these surrogates included POTW samples only.
                                       103B

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 1        SCATTER  OR THE  RESULT  IS  91  PLUS OR MINUS 26; SO
 2        YOU CAN  SEE  FOR THAT REASON  THAT DEUTERATED
 3        CHLOROFORM  IS SIMPLY NOT  A GOOD CHOICE FOR A
 4        SURROGATE.
 5           IF  I COULD  POINT OUT  ANOTHER ONE,  ON THE ACID
 6        FRACTION, THE DEUTERATED  PHENOL.   NOW, THIS DOES
 7        APPEAR  TO BE A  GOOD CHOICE BECAUSE FOR THE SURROGATE,
 8        FOR THE  DEUTERATED PHENOL, THE  AVERAGE WAS 55 PLUS
 9        OR MINUS 20.  FOR THE  NONDEUTERATED COMPOUND THE
10        OVERALL  AVERAGE WAS 54 PLUS  OR  MINUS 24; SO IN THAT
'11        PARTICULAR  INSTANCE YOU SEE  GOOD COMPARISION BETWEEN
12        A NONDEUTERATED AND THE DEUTERATED COMPOUND.
13           DECAFLUOROBIPHENYL is PROBABLY NOT A GOOD CHOICE
14        FOR A SURROGATE, EITHER,  BECAUSE THE RECOVERIES
15        ARE SOMEWHAT LOW.  WE  EXPLAINED THIS AS BEING DUE
16        TO THE  VOLATILITY.  WE SUSPECT  THAT THE LOSSES HERE
17        ARE PROBABLY TAKING PLACE DURING THE KUDERNA'DANISH
18        CONCENTRATION,  BUT  IT  MIGHT  BE  A GOOD CHOICE FROM
19        THE STANDPOINT  OF JUST CONTROLLING KUDERNA~DANISH
20        EXTRACTION OR CONCENTRATION  PROCESSES.  I SUSPECT
21        THAT  IF  YOU  WERE TO LET YOUR EXTRACT GO TO DRYNESS,
22        THAT YOUR RECOVERY WOULD  PROBABLY BE CLOSE TO ZERO
23        FOR DECAFLUOROBIPHENYL.
24
25
                                 JLQ4.

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1            IF WE MOVE ON TO TABLE EIGHT, WE HAVE HERE
2        DIVIDED THE PRIORITY POLLUTANTS, OR AT LEAST THE
3        BASE NEUTRAL PRIORITY POLLUTANTS, INTO TWO GROUPS,
4        ONE GROUP WE CALL THE NONREACTIVE BASE NEUTRAL
5       COMPOUNDS; THE OTHER GROUP WE TERM THE REACTIVE
6       BASE NEUTRAL COMPOUNDS, AND THAT WOULD INCLUDE
7       THINGS SUCH AS BENZIDINE, THE BIS (2-CHLOROETHYL)
8       ETHER, THE PHTHALATES, DIPHENYLHYDRAZINE,
9       HEXACHLOROBUTADINE, HEXACHLOROETHANE AND  ISOPHORONE,
10       THESE ARE COMPOUNDS THAT WE KNOW ARE REACTIVE
11       JUST BASED ON THEIR STRUCTURE,  AND  IF WE GROUP
12       THESE TOGETHER,  YOU DO SEE THAT THE RECOVERIES
13       ARE LOWER AND THE  SCATTER  IS  HIGHER IN MOST CASES,
14           FINALLY,  IF  WE MOVE ON TO TABLE NINE,  I HAVE
15       ATTEMPTED HERE SIMPLY TO SUMMARIZE  SOME  OF THE
16       PROBLEM  COMPOUNDS  AS  FAR AS THE ANALYSES OF THE
17       PRIORITY POLLUTANTS GO,  FOR  EXAMPLE, ANYBODY WHO
18       USES A LARGE  AMOUNT OF DICHLOROMETHANE  IN  THEIR
19       EXTRACTION ROOM  IS PROBABLY GOING TO HAVE  BACKGROUND
20       PROBLEMS IN THEIR  ANALYSES BY THE PURGE  AND TRAP
21       METHOD,   I THINK MOST OF THESE  OTHERS WE HAVE
22       PROBABLY DISCUSSED BEFORE  AT  SOME OF OUR
23       MEETINGS,  SO  NOTHING  REALLY EARTHSHAKING THERE,
24
25
                                   105

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               TABLE VIII.  REACTIVITY GROUPS OF THE B/N PRIORITY POLLUTANTS
                         Method Standard Analysis
Matrix Spiked Analysis

Laboratory
I
II
III
IV
VII
Nonreactive Group
P+Sp
102+26
93+31
-
82+10
^
Reactive Group
P+Sp
86+21
52+46
-
67+18
—
Nonreactive Group
P+Sp
87+18
60^21
58+26
71+12
65+11
Reactive Groin
P+Sp
78+17
64+_25
48+12
63+18
57+17
Nonreactive B/N Compounds:   Acenapthene,  Acenapthylene,  Anthracene,  Benzo(a)anthracene
Benzo(g,h,i)perylene, benzo(a)pyrene,  2-Chloronaphthalene,  1,2-,1,3-.  and 1,4-Dichloro
benzene, 2,6-Dinitrotoluene, Fluoranthene,  Fluorene,  Hexachlorobenze,  Napthalene,
Nitrobenzene, Pyrene, and 1,2,4-Trichlorobenzene.

Reactive B/N Compounds:  Benzidine,  Bis(2-chloroethyl) Ether,  Bis(2-ethylhexyl),
Diethyl, and Dimethyl Phthalates,  1,2-Diphenylhydraxine, Hexachlorobutadi/ie,
Hexachloroethane, and Isophorone.
                                        105A

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      TABLE IX  PROBLEM PRIORITY POLLUTANTS
COMPOUND
Dlchloromethane

bis(chloromethyl)ether
N-nitrosodimethylamine
Di-n-butylphthalate
Bi s-(2-ethylhexyl)phthalate
1,2-diphenylhydrazine
Benzidine
Hexachlorocyclopentadlene
Endrin Aldehyde
Anthracene and Phenanthrene
Chrysene and benzo(a)-
Anthracene
benzo(b)fluoranthrene and
benzo(k)fluoranthrene
        PROBLEM
Frequently found in blanks and
samples because of in lab con-
tamination.
Readily hydrolyzed in water.
Poor chromatographic properties.
Frequently found in blanks.
Frequently found in blanks.
Thermally decomposes to diphenyl
amine and tetraphenylhydrazine.
Poor chromatographic properties.
Subject to thermal  decomposition.
Is readily oxidized.
Coelute on packed columns.
Coelute on packed columns.
Coelute on packed columns.
                     105 B

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 1            IN SUMMARY, WE HAVE LOOKED AT THE  RESULTS  THAT




 2        CAN BE OBTAINED FROM DIFFERENT LABORATORIES  AND WE




 3        FIND THAT THERE IS PRETTY GOOD AGREEMENT  FROM




 4        LABORATORY TO LABORATORY ON THE RECOVERIES OF




 5        STANDARDS ACTUALLY ADDED TO THE SAMPLE OR TO THE




 6        CLEAN MATRIX, AND I THINK IT SHOWS THAT THE  METHOD




 7        THAT WAS SELECTED SEVERAL YEARS AGO WAS,  INDEED,




 8        A SOUND ONE,   THANK YOU,




 9            I WOULD BE HAPPY TO ATTEMPT TO ANSWER ANY




 10        QUESTIONS THAT YOU MIGHT HAVE,




 11




 12




 13



 14




 15




 16



 17




 18




 19




 20




 21




 22




 23




 24




25
                                  JD6_

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                         QUESTION AND ANSWER
                             SESSION
1                                 MR, SPRAGGINS:  SPRAGGINS,
2        RADIAN CORPORATION,  WE HAVE SOME LIMITED DATA ON
3        TWO SAMPLES THAT WERE MADE UP AS SURROGATES AND THEN
4        THEY WERE ANALYZED AT A LATER DATE, AFTER INITIALLY
5        BEING USED, BUT THIS WAS A MUCH LATER DATE, AND WE
6       SEEM TO FIND A PROBLEM WITH THE 2-FLUOROPHENOL
7       AND I WAS JUST WONDERING IF YOU HAD NOTICED THAT,   IT
8       SEEMED LIKE THE CONCENTRATION HAD DROPPED RELATIVE
9       TO THE OTHER COMPOUNDS WITH TIME,  HAVE YOU NOTICED
10       THIS SAME EFFECT?
11                                MR, KLEOBFER:  WHICH COMPOUND?
12                                MR, SPRAGGINS:  IT WAS THE
13        2-FLUOROPHENOL, AND  I MUST  SAY OUR DATA IS LIMITED  AT
14       THIS POINT, BUT IT DID SEEM LIKE THERE WAS A PROBLEM
15       THERE.
16                                MR, KLEOBFER:  WELL, THAT
17       PARTICULAR SURROGATE WAS USED BY A DIFFERENT LABORATORY,
18       OUR OWN LABORATORY,  BY THE  WAY,  IF YOU'RE  INTERESTED,
19        IS  LABORATORY  FOUR;  LABORATORY  FOUR  IN THIS WRITE-UP IS
20       ACTUALLY REGION VII,   I  AM  NOT  GOING  TO REVEAL  THE
21       NAMES  OF THE OTHER  LABORATORIES,   I  SIMPLY DO NOT
22       HAVE ANY EXPERIENCE  WITH THAT PARTICULAR SURROGATE,
23       so  I COULDN'T  COMMENT ON THAT,
24                                MR, BLOOM:   SAUL  BLOOM,  EXXON
25        RESEARCH,   I'VE GOT  A COUPLE OF  QUESTIONS  PERTAINING  TO
                                  107

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 1       TABLE ONE,  As  I UNDERSTAND  IT  FROM THE  FOOTNOTES,
 2       THAT THE LAST COLUMN, THE AVERAGE  WOULD  BE ESSENTIALLY
 3       AN ARITHMETIC AVERAGE OF RECOVERY,  WEIGHTED
 4       ACCORDING TO HOW MANY DATA POINTS  EACH LABORATORY,,,
 5                                MR,  KLEOBFER:   IT'S WEIGHTED
 6       ACCORDING TO THE NUMBER OF DATA POINTS AVAILABLE FROM
 7       THE VARIOUS LABS, RIGHT,
 8                                MR,  BLOOM:   Is  THAT WHAT YOU
 9       DID WITH THE STANDARD DEVIATIONS AS WELL, BECAUSE THAT'S
10       WHAT IT APPEARS TO BE, AND IF  YOU DID,  I  SUGGEST TO  YOU
11       THAT THAT IS NOT THE PROPER WAY,
12                                MR,  KLEOBFER:   THE STANDARD
13       DEVIATION IN THAT CASE WAS COMPUTED BY TAKING AS A
14       DATA POINT THE  RECOVERY FOR EACH INDIVIDUAL COMPOUND BY
15       A PARTICULAR LABORATORY AND SIMPLY  COMPUTING THE
16       STANDARD DEVIATION BASED UPON THAT  INFORMATION,
17                                MR,  BLOOM:   YES,  BUT THE POINT
18       IS THAT THE STANDARD DEVIATION, WHEN YOU 'HAVE MORE  THAN
19       ONE LABORATORY,  IS THE SQUARE  ROOT  OF THE SUM OF THE
20       SQUARES, WHICH MAKES THE NUMBER  PROGRESSIVELY WORSE, NOT
21       BETTER AS YOU'VE REPRESENTED  IT,
22                                MR,  KLEOBFER:   WELL,  YOU
23       HAVE TO REALIZE THAT WE DID MAKE SOME ASSUMPTIONS WHEN
24       WE ATTEMPTED TO TAKE RESULTS  FROM  VARIOUS  LABORATORIES,
25       FOR EXAMPLE, THE SPIKING LEVELS RANGE FROM,,.WELL,  IN

-------
1        THE CASE OF THE VOLATILES, GENERALLY  RANGE  FROM
2       10 TO MAYBE 500 PARTS PER BILLION, SO WE WERE
3       TAKING DATA FROM DIFFERENT LABORATORIES AND
4       DIFFERENT SPIKING LEVELS AND ATTEMPTING TO  LUMP
5       IT TOGETHER,  IT IS JUST AN ATTEMPT TO SUMMARIZE
6       THE RESULTS,
7                               MR, BLOOM:  YES, BUT WHAT
8       YOU HAVE IN TABLE ONE, THE AVERAGE COLUMN,  IS
9       AN ARITHMETIC COMPUTATION FROM THE ONES TO  THE
10       LEFT OF IT, WEIGHTED BY THE NUMBER OF DATA  POINTS,
n       IS THAT NOT CORRECT?
12                               MR, KLEOBFER:  No,
13                               MR, BLOOM:  THAT  is WHAT YOU
14       HAVE DONE WITH THE STANDARD DEVIATIONS AS WELL, OR
15       THAT IS WHAT  IT APPEARS TO BE.
16                               MR, KLEOBFER:  AGAIN,  LET ME
17       TRY TO POINT  OUT AGAIN,  THE STANDARD DEVIATION
18       COMPUTED HERE FOR THE AVERAGE TOOK  INTO ACCOUNT THE
19       RESULT FOR  EVERY COMPOUND FROM EVERY  LABORATORY,
20       IF YOU ARE  INTERESTED  IN SPECIFIC LABORATORIES BY
2i       SPECIFIC COMPOUNDS,  I CAN SUPPLY THAT DATA  TO  YOU,
22       BUT  IN ORDER  TO KEEP THINGS ABBREVIATED,  I  HAVE
23       ATTEMPTED TO  SUMMARIZE  IT THIS WAY,
24                               MR, BLOOM:  WELL,  IF  I MAY,
25
                                 JLQ2_

-------
1       LET ME TRY A SIMPLIFIED CASE,  LET'S  SAY  THAT  I  WAS
2       LABORATORY A AND YOU WERE B AND  I GOT 100 PLUS OR
3       MINUS 5 AND YOU GOT 100 PLUS OR MINUS 15;  THAT
4       DOESN'T MAKE THE AVERAGE OF BOTH OF us 100 PLUS
5       OR MINUS 10, AND THAT'S WHAT TABLE ONE SEEMS TO
6       REPRESENT,
7                                FIR, KLEOBFER:  WELL, WHAT
8       YOU GOT, THOUGH, WAS 100 PLUS OR MINUS  5 OVERALL,  BUT
9       IF YOU LOOK AT THE INDIVIDUAL COMPOUNDS YOU MAY
10       HAVE A 90 PLUS OR MINUS 10, A  70  PLUS OR MINUS 6,
11       AND SO FORTH AND ALL OF THAT WAS INCLUDED  IN THIS
12       COMPUTED STANDARD DEVIATION,
13                                MR, MARRS:   DAVE  MARRS,
14       STANDARD OIL,   A QUESTION, BOB,  Is THIS  DATA ON
15       REPLICATE SAMPLES OR WERE EACH OF THESE SAMPLES
16       SPIKED AND PREPARED IN THE INDIVIDUAL LABORATORIES?
17       IN OTHER WORDS, WAS THE SAMPLE PREPARED AT ONE PLACE
18       AND SENT TO SEVEN LABS AND THAT'S WHERE YOU GET
19       THIS NUMBER FROM?
20                                MR,  KLEOBFER: No, THESE
21       ARE ALL DIFFERENT SAMPLES, THEY REPRESENTED POTW
22       SAMPLES, THEY REPRESENTED SAMPLES FROM THE DETERGENT
23       INDUSTRY, THE TANNING INDUSTRY, ALL TYPES  OF SAMPLE
24       MATRICES WERE INCLUDED HERE.  V/E DID  NOT  ATTEMPT TO
25       COME UP WITH SOME SORT OF UNIFORM   MATRIX,  THE
                                  110

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1        ONLY THING THAT WOULD BE UNIFORM, WELL, WHICH SHOULD
2        BE UNIFORM,  WOULD BE THE METHOD STANDARD, THE
3        STANDARD ADDED TO THE BLANK WATERj EVERYTHING ELSE
4        IS JUST WHATEVER WAS AVAILABLE,
5                                MR, MARKS:   BUT WAS EVEN
6       THE METHOD STANDARD PREPARED IN THE SAME PLACE AND
7       SENT OUT, OR WAS IT PREPARED IN EACH LABORATORY AND
8       THEN THEY WENT AHEAD AND ANALYZED IT?
9                                MR, KLEOBFER:  FOR THE
10       FOUR PRIMARY LABORATORIES THAT SUBMITTED DATA, TWO OF
11       THE LABORATORIES USED THE SAME SPIKING SOLUTIONS,
12       THE OTHER TWO LABORATORIES MADE UP THEIR OWN SPIKING
13       SOLUTIONS,
14                                MR, MARRS:  I GUESS WHAT
15       I'M GETTING AT,AND THEN COMES THE STATEMENT PART,
16       IS ONE OF THE REAL CONCERNS, AND YOU MENTIONED A
17       CORRECTION HERE AT THE HEAD OF TABLE ONE, CHANGING IT
18       FROM INTRALABORATORY TO INTERLABORATORY COMPARISON,
19       MY UNDERSTANDING OF THIS DATA  IS THAT  IT IS REALLY
20       THE PERCENT RECOVERIES, IT  IS  INTRALABORATORY PERCENT
21       RECOVERY,  IT  IS NOT TRUE INTERLABORATORY COMPARISON
22       BECAUSE THEY WEREN'T,,,
23                                MR,  KLEOBFER:  FROM THE
24       STANDPOINT THAT THE LABORATORY PREPARED  ITS OWN
25       STANDARDS, ITS OWN SPIKING  SOLUTIONS,
                                 .111

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 ,                                f'1R, MARRS:  I ASSUME THAT'S
 2       QUALIFIED IN THE TEXT?
 3                                MR,  KLEOBFER:   YES, IT  is,
 4                                MR,  MARRS:   THE  OTHER COMMENT
 5       I HAVE IS ON YOUR PRESENTATION OF  STANDARD DEVIATION,
 6       SHOULDN'T YOU,,,AT LEAST MY UNDERSTANDING  OF  STATISTICS
 7       IS THAT TWO STANDARD DEVIATIONS, ASSUMING  THE DATA
 8       ARE NORMALLY DISTRIBUTED, ENCOMPASSES 95 PERCENT OF THE
 9       VARIABILITY, WHICH IS A PRETTY MUCH ACCEPTED STANDARD,
10       AND IF YOU BEGIN TO DOUBLE THESE STANDARD  DEVIATIONS,
n       YOU'RE PRETTY MUCH AT YOUR PERCENT RECOVERIES IN A LOT
12       OF THE CASES,
13                                MR,  KLEOBFER:  THAT  is TRUE,
14       IN FACT,  IF YOU GO TO THE THREE STANDARD DEVIATIONS
15       THAT EPA RECOMMENDS FOR SOME OF THEIR OTHER PARAMETERS,
16       THAT GIVES YOU A RANGE IN SOME CASES 0 TO  100 PERCENT,
17                                MR,  MARRS:   OR GREATER,
is                                MR,  KLEOBFER:  OR GREATER,WHICH
19       GIVES YOU A LOT OF ROOM FOR ERROR,
20                                MR, STANKD:  GEORGE  STANKO,
21       SHELL DEVELOPMENT,   BOB,  I'D LIKE TO QUOTE ONE  OF YOUR
22       CONCLUSIONS FROM YOUR REPORT, 'WE CAN BE CONFIDENT
23       THAT FALSE POSITIVE ANALYSES ARE CONSIDERABLY LESS LIKELY
24       THAN FALSE NEGATIVE ANALYSES SO THAT WHEN  A PRIORITY
25       POLLUTANT IS DETECTED IN THE ENVIRONMENT WE KNOW THAT
                                .112,

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1        THE MEASURED QUANTITY IS PROBABLY SMALLER THAN THE
2        TRUE VALUE/  THERE WAS A MEETING HERE OF CPIA
3        YESTERDAY,  THERE WAS SOME SLIDES PRESENTED FROM A
4        REPORT, CHEMICAL MANUFACTURERS ASSOCIATION,  I'D
5       LIKE TO PROJECT ONE OF THE SLIDES,
6         THIS SUMMARIZES THE DATA THAT'S INCLUDED IN
7       CHEMICAL MANUFACTURERS REPORT CONCERNING THE BEST
8       METHODOLOGY, ACCORDING TO YOUR REPORT, THE VOLATILE
9       ORGANICS, WHICH WE CONCUR WITH YOU, THIS SLIDE,
10       THE WAY IT'S PRESENTED, SHOWS THE TIMES THAT WE HAVE
11       QUALITATIVE AGREEMENT OR DISAGREEMENT BETWEEN EPA
12       LABS VERSUS COMPANY LABS,  THE NUMBER 656 REPRESENTS
13       THOSE TIMES WHEN THE EPA LAB AND THE COMPANY LAB
14       AGREED THAT A COMPOUND WAS NOT PRESENT IN A PARTICULAR
15       ENVIRONMENTAL SAMPLE.  THE BOTTOM RIGHT-HAND CORNER,
16       THE 132, IS THE NUMBER OF TIMES THAT THE EPA LAB AND
17       THE COMPANY LAB BOTH AGREED THAT THE COMPOUND WAS IN
18       THE ENVIRONMENTAL SAMPLE,  THE DIAGONAL, THE 656 AND
19       THE 132; INDICATE THE TIMES WE AGREE QUALITATIVELY,
20       THE UPPER RIGHT-HAND CORNER, THE EPA DETECTED COMPOUNDS
21       IN THEIR SAMPLES  132 TIMES THAT THE COMPANY LABORATORIES
22       DID NOT,  CONVERSELY, THE COMPANY LABORATORIES FOUND
23       COMPOUNDS 55 TIMES THAT WERE NOT REPORTED BY THE EPA
24       LABORATORIES; THAT PARTICULAR DIAGONAL REPRESENTS THE
25       AMOUNT OF DISAGREEMENT ON WHETHER A COMPOUND  IS

-------
 ,       QUALITATIVELY PRESENT OR NOT PRESENT,  THE  CMA




 2       HAS NOT TRIED TO IDENTIFY THESE AS FALSE  POSITIVES




 3       OR FALSE NEGATIVES,  OUR OWN WORK AT SHELL, WE




 4       HAVE INDICATED THAT THERE IS CONSIDERABLE DISAGREEMENT




        QUALITATIVELY ON WHETHER A COMPOUND IS PRESENT
 D



 6       OR NOT,  TO QUOTE SOME DATA THAT HAS BEEN RELEASED



 7       TO THE AGENCY, THREE COMPETENT LABORATORIES ANALYZED



        THE SAME SPLIT SAMPLE; OF THE 38 COMPOUNDS  THAT WERE
 O



 9       REPORTED BY ONE OF THE THREE LABORATORIES,  THERE



10       WERE ONLY FOUR COMPOUNDS THAT ALL THREE LABORATORIES




n       AGREED WERE THERE.



12         I HAVE NOT TRIED TO IDENTIFY THESE AS FALSE



13       POSITIVES OR FALSE NEGATIVES; I DON'T KNOW WHAT THEY



14       ARE,   I HAVE NOT SEEN ANYTHING IN YOUR REPORT THAT



15       CLEARS UP THIS PARTICULAR PROBLEM,YET SOMEHOW YOU ARE




16       ABLE TO MAKE A STATEMENT THAT THE POSSIBILITY OF A



17       FALSE POSITIVE IS RATHER REMOTE,  COULD YOU EXPLAIN



18       HOW YOU CAME TO THAT CONCLUSION?



19                                m. KLEOBFER:  WELL, GEORGE,




20       I THINK IF YOU WERE TO QUALIFY YOUR DATA AND JUST



21       LIMIT YOURSELF TO THOSE COMPOUNDS THAT ARE  PRESENT IN




22       A REASONABLE QUANTITY, AND LET'S SAY, IN THE  CASE OF THE



23       VOLATILES, AT 20 PARTS PER BILLION OR ABOVE, I THINK




24       YOUR TABLE WOULD HAVE LOOKED QUITE DIFFERENT THAN




25       WHAT IT DID,  IN OTHER WORDS, HOW MANY OF THESE
                                 JUA

-------
1       DATA  POINTS  ARE  DUE  TO LOW LEVELS OF VOLATILES WHERE
2       THERE'S MORE LIKELY  TO BE  A MISTAKE?
3                                MR,  STANKO:  MOST OF THE DATA
4       POINTS WERE  10  PARTS PER BILLION OR LESS, WHICH IS SORT
5      OF  THE ASSUMED  LIMIT OF DETECTION., IF YOU WANT TO CALL
6      IT  THAT,   THE HIGHER PERCENTAGE OF THESE VALUES INCLUDED
7      ON  THESE  TABLES  ARE  IN THE HIGHER RANGE AT 20 PLUS,
8      WE  CONCUR WITH  WHAT  YOU HAVE REPORTED HERE ON THE USE
9      OF  THE FLUORINATED SURROGATES; WE HAVE EXPERIENCED
10      THE SAME  PROBLEMS THAT YOU HAVE.  WE ALSO CONCUR,IF YOU
11      TAKE  DISTILLED  WATER AND ADD THE COMPOUNDS IN,THAT THE
12      RECOVERIES ARE  VERY  SIMILAR, BUT WE DO NOT CONCUR IF
13      YOU TAKE  OUR PARTICULAR MATRIX-TYPE SAMPLES THAT YOU
14      WILL GET  AS HIGH A RECOVERY AS YOU DO IN DISTILLED WATER,
15                               MR,  KLEOBFER:  OKAY, BUT YOU'D
16      DISAGREE  WITH THE ONE STATEMENT,
17                                MR, STANKO:  I WOULD DISAGREE
18      WITH THE  ONE STATEMENT BECAUSE  I SEE NOTHING  IN THIS
19       PARTICULAR REPORT THAT ALLOWS YOU TO COME TO THAT
20       PARTICULAR CONCLUSION,  I  AM STILL ON BLOCK NUMBER ONE,
21      WHICH TELLS ME THAT THERE  IS DISAGREEMENT, BUT I CANNOT
22      DISTINGUISH BETWEEN FALSE  POSITIVES OR FALSE NEGATIVES,
23      AND I DON'T SEE HOW YOU CAN, EITHER, AND MAKE THIS
24       PARTICULAR STATEMENT,
25                                MR,  KLEOBFER:   WELL,  I STAND
       BY  MY STATEMENT,1  WE  DISAGREE,
   	115	

-------
 1                                 MR,  TELLIARD:  OUR NEXT
 2        SPEAKER  is  WALT  SHACKELFORD  FROM ATHENS,  As YOU KNOW,
 3        WHEN WE  STARTED  THIS  PROGRAM,ONE OF OUR ATTEMPTS WAS
 4        TO, SINCE WE'RE  SPENDING  THIS  TRIG-A-BUCK PER
 5        SAMPLE ANALYSIS, WAS NOT TO  THROW THE DATA AWAY
 6        LOOKING  FOR 1, 2-DIPHENYL BAD  STUFF; SINCE WE WERE
 7        GOING TO GET OUR HANDS ON A SAMPLE, WE'D LIKE TO GET
 8        AS MUCH  UTILITY  OUT OF IT AS  POSSIBLE, AND THEREFORE,
 9        IT WAS DECIDED EARLY  ON THAT THE TAPES WOULD BE
10        STORED AND  SENT  OFF TO ATHENS  FOR LATER EXAMINATION,
         AS WELL  AS  THE EXTRACTABLE  CONCENTRATES,
12         OVER THE  LAST  YEAR, NOW,  VJALTER HAS BEEN WORKING ON
13        PUTTING  A PROGRAM TOGETHER  AND GETTING TRIAL
14        RUNS AT  IT  AND BASICALLY  WHAT  HE'S GOING TO TALK
15        ABOUT TODAY IS THE STATUS AND  UPDATE ON THE MASS
16        SPECTRAL DATA PROGRAM,
17
18
19
20
21
22
23
24
25
                                  116

-------
              EXAMINATION  OF  MASS  SPECTRAL DATA TAPES
1            FOR CHARACTERIZATION OF SAMPLE COMPOSITION
2                     BY:   WALTER  SHACKELFORD
3       AS BILL MENTIONED. WE HAVE HAD A  PROJECT FOR ABOUT
4       A YEAR AT ATHENS TO BEGIN TO SURVEY THE RAW DATA
5       THAT'S BEEN SAVED ON MAGNETIC TAPE FROM THE SCREENING
6       PHASE OF THE  PRIORITY POLLUTANT PROGRAM,  IF I COULD
7       HAVE THE FIRST SLIDE. I'D LIKE TO GO THROUGH SOME
8       MATERIAL THAT MIGHT BE A LITTLE REDUNDANT. BUT IT
9       WILL GIVE THE RATIONALE FOR THE PROGRAM AS WE HAVE
10       IT,  FOR THOSE OF YOU THAT ARE NOT AWARE OF IT. THE
11       CONSENT DECREE. AS IT WAS SIGNED  IN JUNE OF '76.
12       LISTED 65 COMPOUNDS AND COMPOUND  CLASSES,  PRETTY
13       EARLY  IN THE  GAME  IT WAS RECOGNIZED THAT TO LOOK FOR
14       EVERY COMPOUND IN  EACH CLASS WOULD BE  A TASK THAT
15       WAS BEYOND THE SCOPE OF THE RESOURCES  THAT WERE AVAIL'
16       ABLE,  THROUGH A  PROCESS OF SELECTION  THAT INVOLVED
17       LOOKING AT WHAT COMPOUNDS WERE MANUFACTURED  IN
18       QUANTITY OR WHAT  HAD BEEN FOUND BEFORE. THE LIST
19       WAS RESOLVED  INTO  THE COMPOUND LIST THAT WE RECOGNIZE
20       NOW AS THE PRIORITY  POLLUTANTS,   THE SPECIFICS ON
21       THAT  RESOLUTION WERE PUBLISHED IN PROCEEDINGS OF A
22       PETROLEUM REFINERY WASTEWATER MEETING  IN 1977 AND
23       THEN  AGAIN IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
24       LAST  YEAR,
25
            SLIDE  2  PLEASE,   THE  ANALYSIS  PROGRAM HAD  TO  BE
                                  JLU.

-------
                    CONSENT DECREE
                         65
                  CHEMICAL CLASSES
  114
SPECIFIC
ORGANICS
13
METALS

CYANIDE
ASBESTOS
                           117A

-------
                   ANALYSIS PROGRAM

A,  ORGANIC ANALYSIS ACCOMPLISHED BY GC/MS --
      RAW DATA SAVED ON MAGNETIC TAPE
B,  AFTER INITIAL ANALYSIS FOR 114 ORGANICS,
      MAGNETIC TAPE IS SURVEYED FOR OTHER
      ORGANICS
C,  EXTRACTS OF EACH SAMPLE SAVED FOR LATER
      STUDY
                             117B

-------
DESIGNED TO TAKE INTO ACCOUNT THE FACT THAT WE ARE
NOT LOOKING FOR EVERY COMPOUND IN EVERY GROUP,  WE
ARE LOOKING FOR A FEW SPECIFIC ONES,  SlNCE IT HAD
BEEN DECIDED THAT GS/MS WAS TO BE USED/ WE WOULD
SAVE ALL THE RAW DATA IN COMPUTER READABLE FORM,
THUS, IF SOME OTHER COMPOUNDS BECAME OF INTEREST
LATER, WE COULD GO BACK AND SEARCH THIS DATA,
   ALSO, TO PROVIDE CONFIRMATION, EACH EXTRACT FROM
EACH SAMPLE WOULD BE SAVED FOR LATER REANALYSIS,
WE HAVE A PROGRAM FOR CONFIRMATION THAT HAS JUST
GOTTEN UNDER WAY,  IT SOON BECAME APPARENT THAT
THE MAGNITUDE OF DATA THAT WAS GOING TO BE SAVED
ON MAGNETIC TAPE MADE IT PRACTICALLY IMPOSSIBLE
TO GO THROUGH THE DATA MORE THAN ONE TIME IN THE
COMPUTER SURVEY,  So THE IDEA BECAME TO SURVEY
THE TAPES FOR EVERY COMPOUND THAT WE CAN FIND
USING STATE OF THE ART COMPUTERIZED DATA REDUCTION,
THE FINALIZED PROGRAM BECAME A STUDY TO LOOK FOR
EVERY COMPOUND THAT CAN BE FOUND BY COMPUTERIZED
SPECTRUM MATCHING TECHNIQUES,  THEN GET THE MATCHER
CONFIRMED,  IF POSSIBLE, BY REANALYZING THE EXTRACT,
AND LIST THOSE COMPOUNDS FOR FUTURE GUIDELINES OR
REGULATIONS,
   SLIDE 3 PLEASE.   OUR PROJECT OBJECTIVES WERE TO
BUILD AND REFINE THE GC/MS DATA SYSTEM THAT WAS
                        118

-------
                  PROJECT OBJECTIVES


A,  BUILD AND REFINE GC/MS DATA SURVEY SYSTEM

B,  PROVIDE EFFICIENT IDENTIFICATION OF ORGANIC
    COMPOUNDS IN GC/FIS DATA

C,  GATHER STATISTICS OF SELECTED IDENTIFIED AND
    UNIDENTIFIED ORGANIC COMPOUNDS BY INDUSTRIAL
    CATEGORY

D,  BUILD HISTORICAL LIBRARY

E,  MEET MILESTONE SCHEDULE
                         118A

-------
 1        NECESSARY TO SURVEY THIS DATAj TO PROVIDE SOME
 2        EFFICIENT MEANS  OF IDENTIFICATION OF THESE ORGANIC
 3        COMPOUNDS WITHOUT HAVING A CHEMIST SIT DOWN AND
 4        LOOK AT EVERY SPECTRUM;  THEN COLLECT STATISTICS ON
 5        BOTH THOSE SPECTRA WHICH HAVE BEEN TENTATIVELY IDEN-
 6        TIFIED  AND ALSO  KEEP STATISTICS ON THOSE SPECTRA
 7        THAT ARE NOT MATCHED IN  THE LIBRARY BY MATCHING
 8        THEM AGAINST EACH OTHER  TO FIND THOSE REOCCURRING
 9        SPECTRA THAT WE  DO NOT HAVE ANY REFERENCES FOR,
10           WE WANTED TO  BUILD A  HISTORICAL LIBRARY THAT
11        WOULD INCLUDE ALL OF THE COMPOUNDS THAT WE ARE
12        FINDING,  THEIR GC RETENTION TIMES AND THEIR SPECTRA,
13        THUS, IN FUTURE  USE, THE MATCHING PROCESS BECOMES
14        MORE DEFINITIVE  BECAUSE  ONE KNOWS A RETENTION TIME
15
         FOR  THESE  COMPOUNDS,   FINALLY,  WE  WANTED TO BE ABLE
16        TO  MEET  OUR  MILESTONE  SCHEDULE  (
            THIS  SCHEDULE  WAS  PUT  FORTH  WELL BEFORE WE HAD  ANY
         FUNDS, PEOPLE,  OR ANY  KNOWLEDGE THAT ANYONE WOULD  LET
19                           ,,
         US  DO THE  PROJECT,  WE MADE  THE FIRST MILESTONE AND
20
         THE SECOND MILESTONE,   OUR THIRD MILESTONE IS ONE
         YEAR'S WORK  AT  FULL SPEED IN WHICH WE ARE TO ANALYZE
         10,000 GC/MS RUNS BY OUR  COMPUTER METHODS,
            THE GTH SLIDE  SHOWS HOW WE'RE FARING RIGHT NOW,
         AT  THE PRESENT  TIME WE'VE GONE  THROUGH 3,200 GC/MS
25
         RUNS AND HAVE LOOKED AT SAMPLES FROM ALL 21

-------
                MILESTONES





  100    GC/MS RUNS ANALYZED      APRIL L 1979



 1000    GC/MS RUNS ANALYZED      SEPT, L 1979



10,000   GC/MS RUNS ANALYZED      SEPT, 1, 1980



20,000   GC/MS RUNS ANALYZED      SEPT, 1, 1981
                              119A

-------
                    PROJECT STATUS

> 3200           DATA FILES PROCESSED
                   AS OF JANUARY 4,  1930

    21           INDUSTRIAL CATEGORIES
                   INCLUDED

 *  20%          IDENTIFICATION EFFICIENCY
                   (AVERAGE 4 MONTHS)
                              119B

-------
1        INDUSTRIAL CATEGORIES,  OUR IDENTIFICATION EFFICIENCY,
2        THAT IS WHAT FRACTION OF THE SPECTRA CHOSEN FOR MATCH-
3        ING ARE MATCHED, IS ABOUT 20 PERCENT,  As WE MOVE ALONG
4        I'LL SHOW YOU HOW THAT FIGURE SHOULD IMPROVE,  IN TALK-
5       ING WITH DR, STEPHEN HELLER, WHO SPONSORED THE BUILDING
6       OF THE EPA-NIH DATA BASE, IN CROSS-CHECKING COMPOUNDS
7       I WAS INFORMED THAT ONLY ABOUT 12 PERCENT OF THOSE
8       COMPOUNDS KNOWN TO BE MANUFACTURED IN INDUSTRY ARE
9       FOUND IN THE LIBRARY OF SPECTRA,
1°          SLIDE 7  PLEASE.  THIS is A PROFILE OF THE DATA WE
11       HAVE LOOKED AT  IN TERMS OF  INDUSTRIES,  THE CATEGORY
12       N/A TAKES INTO ACCOUNT STANDARD RUNS  AND THOSE
13       SAMPLES FOR WHICH THE CONTRACTOR WHO ANALYZED THEM
14       DID NOT KNOW THE  INDUSTRIAL CATEGORY,  THE DIFFERENCES
15       IN PERCENTAGES HERE ARE REALLY ONLY  FORTUITOUS; THEY
16       JUST HAPPEN TO BE THE-RUNS  THAT WE LOGGED  IN FIRST,
17       NOW, THE COMPUTER PROGRAM  IS BUILT AROUND  ABOUT FIVE
18       MAJOR PORTIONS,  THE  FIRST  PORTION,  WHICH  IS TURNED
19       ABOUT TO BE THE MOST  TIME-CONSUMING,  IS THE  INVENTORY
20       PROCESS,  WE ARE  PRESENTLY  USING THE INFORM DATA BASE
21       MANAGEMENT  SYSTEM TO  TAKE CARE OF OUR  INVENTORY,
22          SECOND,  WE  HAVE THE DATA ANALYSIS PART  OF THE
23       SYSTEM, WHICH  INVOLVES THREE MAJOR COMPUTER  PROGRAMS,
24       THE  CLEANUP PROGRAM,  WHICH  WAS DEVELOPED BY  TOM
25       RlNDFLEISCH AND HIS  CO-WORKERS AT STANFORD UNIVERSITY,
                                 JL20_

-------
 PROFILE OF SAMPLES ANALYZED
      BY INDUSTRIAL CODE
          (1/10/80)
           Industry
15.811    Public Owned Treat Works
11.17%    Pulp § Paper
 7.521    Foundries
 7.151    Paint $ Ink
 6.941    Organic Chemicals
 6.891    Auto § Other Laundries
 6.111    Inorganic Chemicals
 5.64%    Coal Mining
 3.911    Electronics
 3.08%    Mechanical Products
 2.24%    Pesticides Mfg.
 2.19%    N/A
 2.09%    Pharmaceuticals
 2.04%    Printing § Publishing
 1.83%    Transportation Equipment
 1.77%    Nonferrous Metals
 1.62%    Plastics § Synthetics
 1.571    Textile Mills
 1.57%    Rum Industry
 1.46%    Rubber Processing
 1.41%    Photographic Industries
 1.20%    Porcelain/Enameling
 1.04%    Leather Tanning
  .78%    Industry Unknown
  .73%    Organics § Plastics
  .73%    Amusements § Athletic Goods
  .68%    Plastics Mfg.
  .57%    Ore Mining
  .16%    Steam Electric
  .05%    Timber Products
  .05%    Petroleum Refining

                     120A

-------
1        LOOKS AT GC/MS DATA AND EXTRACTS MASS SPECTRA WHERE
2        IT SEES PEAKING OF A CERTAIN NUMBER OF IONS WITHIN
3        A TWO SCAN WINDOW, EXTRACTS THAT SPECTRUM AND PASSES
4        IT ON TO THE THIRD LARGE PART OF THE PROGRAM, THE
5       PROBABILITY BASED MATCHING SYSTEM,  THIS MATCHING
6       SYSTEM WAS DEVELOPED BY FRED MCLAFFERTY AT CORNELL,
7       MUCH OF THE DEVELOPMENT WORK WAS DONE UNDER A GRANT
8       SPONSORED BY THE ATHENS LABORATORY,  THE FOURTH PART
9       IS THE HISTORICAL LIBRARY,  MANY  IDEAS IN PART CAME
10       FROM, AGAIN, WORK AT STANFORD UNIVERSITY FROM DENNIS
11       SMITH, TOM RINDFLEISCH, AND BILL  FITCH,  THIS PART
12       OF THE PROGRAM TAKES OUR ANSWERS  (THOSE SPECTRA THAT
13       ARE  MATCHED WITHIN OUR  SPECIFICATIONS), PUTS THEM
14       INTO A DATA BASE  MANAGEMENT SYSTEM ALONG WITH THE
15       GC RETENTION TIME, THE  INDUSTRY FROM WHICH THE SAMPLE
16       CAME, AND THE  ANALYTICAL  CONTRACTOR THAT COLLECTED
17       THE  DATA ORIGINALLY,
18          A FINAL  PART  IS UNKNOWN, OR  MISS LIBRARY,  THIS
19       LIBRARY ALSO  KEEPS SIMILAR STATISTICS  TO THOSE  IN  THE
20       HISTORICAL  LIBRARY,  BUT CONCERNS ITSELF  ONLY WITH
21       THOSE  SPECTRA  THAT HAVE NOT BEEN IDENTIFIED  BY
22        SPECTRUM  MATCHING,   IN  THAT WAY WE'RE  ABLE TO FIND
23        REOCCURRING UNMATCHED SPECTRA AND PRIORITIZE THEM
24        FOR  SOME  SORT OF ANALYSIS IN  WHICH WE  WOULD  USE MORE
25        EXTENSIVE  ANALYTICAL TECHNIQUES ON THE SAVED EXTRACT
                                -12L

-------
 1        SUCH  AS  HIGH  RESOLUTION  MASS SPEC OR GC/FTIR,
 2           SLIDE 8  PLEASE.   I'D  LIKE TO GO THROUGH THE
 3        CLEANUP  PROGRAM BRIEFLY,   IF YOU'RE INTERESTED IN
 4        READING  ABOUT IT,  THERE  WAS  A PAPER BY RlNDFLEISCH
 5        IN  JULY  OF  '77 IN  ANALYTICAL CHEMISTRY,   CLEANUP
 6        DETECTS  COMPONENTS  THAT  ELUTE AT LEAST TWO SCANS
 7        FROM  EACH OTHER AND SUBTRACTS LOCAL BACKGROUND
 8        THAT  IT  CALCULATES  FOR EACH  MASS,   IT THEN APPLIES
 9        A SYMMETRY  OR PEAK  BROADNESS SCREEN ON PEAKS SUCH THAT
10        COLUMN BLEED, WHICH NORMALLY IS GOING TO EXHIBIT A
11        BROAD PEAK, WOULD  BE ELIMINATED,   UNFORTUNATELY,  IF
12        A COMPONENT OF INTEREST  HAS  A BROAD PEAK,  THEN IT
13        GETS  ELIMINATED ALSO,  CLEANUP WAS WRITTEN ORIGINALLY
14        TO  BE AN INTERACTIVE PROGRAM WHERE ONE VARIES THE
15        PROGRAM  PARAMETERS  TO GET  THE MOST ACCURATE FIT
16        OF  THE DATA,   OF COURSE, WE  DON'T HAVE THAT
17        LUXURY;  WE  DO NOT  OPERATE  IT INTERACTIVELY, AND
18        WE'RE PRESENTLY TRYING TO  CHANGE THE SYSTEM
19        SUCH  THAT WE  COULD  DYNAMICALLY VARY SOME OF THESE
20        PARAMETERS  DURING  COMPUTER ANALYSIS,
21           SLIDE 9  PLEASE.   THIS  is  AN EXAMPLE OF  RESULTS IN
22        THE EASIEST CASES,   I'M  NO DIFFERENT FROM  ANYBODY
23        ELSEj THESE ARE THE ONLY ONES I SHOW WHEN  I GIVE
24        A TALK.   HERE WE HAVE A  PICTURE OF THE H-PHENOL
         MIXTURE  THAT  MOST  OF THE PEOPLE IN THE ROOM HAVE
                                  99

-------
                       CLEANUP





A,  DETECTS COMPONENTS ELUTING 2 OR MORE SCANS APART



B,  SUBTRACTS BACKGROUND FOR EACH MASS



C,  ELIMINATES COLUMN BLEED
                              122A

-------
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-------
        RUN ON TENAX,  NOTICE THE PEAK THAT HAS SCANS 215
2       AND 217 MARKED,  LOOKS LIKE A NICE SYMMETRICAL PEAK
3       WITH ONLY ONE COMPONENT,
           SLIDE 10,  AFTER RUNNING THROUGH THE CLEANUP
5       PROGRAM WE FIND THERE ARE ACTUALLY TWO COMPONENTS,
6       ONE WHICH IS 0-NITROPHENOL, THE OTHER ONE DIMETHYL-
7       PHENOL,  THE REFERENCE SPECTRA ARE PRINTED UP IN
8       THE CORNER OF THE SLIDE,  THIS IS, OF COURSE, AN
9       IDEAL CASE,
10

        COMPARED TO A HUMAN SITTING AT A TERMINAL DOING
           SLIDE 11.  STATISTICS CONCERNING HOW CLEANUP
11
12       MANUAL PEAK FINDING AND BACKGROUND SUBTRACTION
13       WERE COLLECTED,  OUR OBJECTIVE FOR THE COMPUTER
14       PROGRAMS IS TO DUPLICATE THE ROUTINE OPERATOR
15       OPERATING MANUALLY AT A TERMINAL,  IN MANUAL PEAK
16       FINDING, THE OPERATOR IN THESE CASES SAW THE NUMBER
17       OF PEAKS SHOWN IN THE LEFT-HAND COLUMN,  OF THOSE
        NUMBERS OF PEAKS HE WAS ABLE TO FIND AFTER SUBTRACTING
        BACKGROUND AND SEARCHING WITH HIS COMPUTER TO MATCH
20
        SPECTRA, HE WAS ABLE TO IDENTIFY THE NUMBER OF COM~
21       POUNDS SHOWN IN THE NEXT COLUMN,  IN RUNNING CLEANUP,
        WE FOUND THE NUMBER OF COMPONENTS SHOWN IN THE THIRD
23       COLUMN,  THE NUMBER OF IDENTIFICATIONS IS SHOWN IN THE
        FINAL COLUMN,  FOR INSTANCE, IN SAMPLE NUMBER ONE,
        CLEANUP-PBM IDENTIFIED 13 COMPONENTS THAT WERE THE
                                JL23_

-------
Example of CLEANUP Program Output for near co-eluting compounds (SCAN 215, 2-nitrophenol and
SCAN 217, 2,4-dimethylphenol).  Spectra acquired under GC/WS conditions of protocol.
SCANTIME « 3.0 sec.
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-------
               PEAK FINDING

    MANUAL                     CLEANUP-PBM
PEAKS     ID'S               PEAKS     ID'S

 30        18                 46        18(6)
 18         7                 44         7(4)
 31        11                 41        11(2)
 26        10                 43        10(2)
                       123B

-------
         SAME AS WERE FOUND MANUALLY,  THEN   CLEANUP-PBM
 o
         IDENTIFIED 6 ADDITIONAL COMPONENTS,   As  YOU LOOK

         DOWN THE LIST. YOU'LL SEE THAT WE WERE ABLE TO
 4
         DUPLICATE THE IDENTIFICATIONS THAT THAT  MANUAL MODE

         WAS MAKING,  WE ALSO WERE ABLE TO FIND A FEW MORE,

         HOWEVER. AS YOU CAN TELL BY LOOKING  AT THE  SLIDE. OUR
 7
         PERCENTAGE OF IDENTIFICATIONS DROPPED CONSIDERABLY,

         THE DATA DISPLAYED ON THE SLIDE  IS BETTER THAN  OUR
 9
         AVERAGE. SINCE THIS DATA WAS ACQUIRED USING CAPILLARY

         COLUMNS,  THUS. WE HAD BETTER RESOLVED PEAKS TO WORK
 11
         WITH,
 12
            SLIDE 12. PLEASE.   THE PROBABILITY BASED MATCHING
 13
         SYSTEM WAS CHOSEN FIRST OF ALL BECAUSE IT S A REVERSE

 14                it
         SEARCH,  WE KNEW THAT WE WERE GOING  TO GET  A LOT OF
 15
         MIXED  SPECTRA. AND REVERSE SEARCHING ALLOWS ONE TO
 16
         LOOK FOR THE KNOWN SPECTRUM IN THE UNKNOWN  SPECTRUM,
 17
         THE ADVANTAGE COMES IN WHERE ONE HAS A SPECTRUM THAT S
 18
         ACTUALLY THE SUM OF TWO DIFFERENT SPECTRA,   ONE  IS
 19
         ABLE TO GET A GOOD FIT FOR THE KNOWN DESPITE THE
 20
         PRESENCE OF OTHER MASSES DUE TO  IMPURITIES,   IN
 21
         MANY CASES ONE CAN GET TWO GOOD  MATCHES  FOR TWO
 22
         DIFFERENT COMPONENTS IN THE SAME SPECTRUM,   THOSE
 23
         OF YOU THAT USE THE FlNNIGAN " INCOS SYSTEM KNOW THAT
 24
         THERE  IS A REVERSE SEARCH CAPABILITY THERE  THAT WILL
25
         ALLOW  YOU TO DO THE SAME THING,  I BELIEVE  THE  HEWLETT'
                                JL24.

-------
                         PBM





A,  REVERSE SEARCH-LOOKS FOR  REFERENCE IN UNKNOWN



B,  SEVERAL MATCH PARAMETERS FOR EVALUATION OR FIT
                             124A

-------
 1       PACKARD SYSTEM SUPPLIES PBM WITH  IT,
 2          ONE THING WE LIKED ABOUT PBM IS THAT THERE ARE
 3       A NUMBER OF PARAMETERS THAT LET ONE EVALUATE THE FIT,
         THERE'S A GENERAL OVERALL QUALITY OF THE MATCH;
 5       THE DIFFERENCE FROM A PERFECT MATCH SCOREj WHETHER
 6       OR NOT THE MOLECULAR ION WAS FOUNDj HOW MANY PEAKS
 7       OF THE KNOWN WERE NOT OBSERVED IN THE UNKNOWN,
 8
         THESE PARAMETERS ALL HELP IN DECIDING WHETHER OR
         NOT ONE HAS A GOOD MATCH.  ANOTHER REASON FOR USING

 10       PBM WAS THAT IT HAD BEEN EVALUATED IN THE LITERATURE

 11       AND WAS SHOWN TO BE EQUAL TO OTHER MATCHING SYSTEMS

 12       IN TERMS OF FORWARD SEARCHING, THAT IS, IN TERMS

         OF ONE COMPONENT MATCHING,  AND CERTAINLY SUPERIOR

         IN TERMS OF MIXTURES,

            SLIDE 13, PLEASE,   Now,  HERE WAS AN INTERESTING

         POINT WE RAN INTO,   V/E  FOR SOME TIME  HAD BEEN USING
 17
         DIFFERENT DATA BASES IN OUR LABORATORY FOR MATCHING,
 18
         ONE IS A COLLECTION OF SPECTRA THAT WERE MORE OR LESS
 19
         HAPHAZARDLY PUT TOGETHER AND CONTAINED, ONCE THE
 20
         DEUTERATED COMPOUND SPECTRA AND THOSE COMPOUNDS WITH
 21
         MOLECULAR WEIGHT OVER  450 WERE TAKEN OUT,  ABOUT
 22
         37,000 SPECTRA,   ANOTHER LIBRARY WE HAD AVAILABLE
 23
         TO US WAS A DATA BASE  WITH ABOUT 32,000 DIFFERENT
 24
         SPECTRA,   OUR DATA BASE OF 37,000 ACTUALLY DOES
25
         HAVE 32,000 DIFFERENT  SPECTRA, BUT IT ALSO HAS MANY
                                .121.

-------
Ln
                           DATA BASE RECALL


DATA BASE I                   DATA BASE II                   MANUAL ID

TOLUENE (75+)                 TOLUENE (75+)                 TOLUENE

7-OXABICYCLO 2,2,1            2-CYCLOHEXENE-l-              2-CYCLOHEXENE-l-OL
   HEPTANE W9+)                 OL (76+)

PHTHALIDE (56, -2)             METHYL BENZOATE (69+)          METHYL BENZOATE

HEXACOSANOIC ACID             OCTADECANOIC  ACID (105+)       OCTADECANOIC ACID
   (102, -3)

-------
 1       DUPLICATE SPECTRA,   IT HAS BEEN  OUR  OPINION  AND THAT

 2       OF SOME OTHER PEOPLE THAT DUPLICATE  SPECTRA  WILL AID

 3       IN MATCHING, SINCE THEY MANY TIMES CAN  TAKE  INTO

        ACCOUNT THE DIFFERENCES IN INSTRUMENTATION,   DATA

 5       BASE  I WAS OUR SPECTRUM LIBRARY  OF SOME 32,000

 6       SPECTRA WITH NO DUPLICATE SPECTRA,   THESE  ARE THE

        BEST  MATCHES DELIVERED BY PBH   DATA BASE  II  IS THE

 8       LIBRARY THAT HAS MANY DUPLICATE  SPECTRA,   USING DATA

        BASE  IIj WE FIND DIFFERENT COMPOUNDS AS THE  BEST
10                                               T   T
        MATCH FROM THOSE FOUND USING DATA BASE  I,  THE  MANUAL

        IDENTIFICATION AGREED WITH DATA  BASE II AND  IN  A

        COUPLE OF CASES DID  NOT AGREE WITH DATA BASE  I,   WHY

        DID THIS HAPPEN?  WELL, DATA BASE I  DID NOT  GIVE YOU
14
        A CHOICE, FOR INSTANCE, OF METHYLBENZOATE  SPECTRA

        SINCE IT ONLY HAD ONE.  To BE SURE,  IN  DATA  BASE II
16
        WE HAD THE SAME SPECTRUM OF METHYLBENZOATE THAT WAS

        IN DATA BASE I,  HOWEVER, AS YOU MIGHT  WELL  IMAGINE,
18
        THE SPECTRUM THAT WAS IN BOTH DATA BASE I  AND IN DATA
19
        BASE  II GAVE A POOR  MATCH,  IN DATA  BASE  II  WE  HAD
20
        SEVERAL METHYLBENZOATE SPECTRA AND WE GOT  A  MUCH
21
        BETTER MATCH USING THEM,
22
           SLIDE 14,  THE NEXT THING WE  WANTED  TO  LOOK  AT
23
        WAS RELATIVE RETENTION TIMES,  As YOU KNOW,  A MAJORITY
24
        OF THE ANALYSIS DONE  IN THIS SCREENING  PHASE WAS DONE
25
        USING VERY SIMILAR CONDITIONS,   IN FACT, WE  HAD
                                 126.

-------
             USE OF RETENTION TIMES

    COMPOUND         RANGE OF RRT     RANGE OF K

DIOCTYLPHTHALATE          0,03          US - 100
PHTHALIDE                 0,01          57-77
TOLUIC ACID               0,03          48 - 85
                            126A

-------
 1        ACTUALLY ASKED THAT THEY ALL BE RUN UNDER THE SAME

 2        CONDITIONS,   IN TAKING A LOOK, WE FELT THAT IF WE

 3        GOT A SPECTRUM MATCH OF SUFFICIENT QUALITY (DEFINED

         EMPIRICALLY)  PLUS  A RELATIVE RETENTION TIME MATCH

 5        WITHIN A VERY CLOSE WINDOW (ALSO DETERMINED EMPIRICALLY)
                                                                j

         WE  COULD SEND THAT DATA TO THE HISTORICAL LIBRARY

         WITHOUT THE  INTERFERENCE OR THE HELP OF A CHEMIST,

 8        OF  COURSE,  IF EITHER THE RETENTION TIME OR THE

         SPECTRUM MATCH WAS NOT GOOD, THEN WE WOULD HAVE

10        TO  HAVE A CHEMIST  TO EVALUATE THE DATA,   IF YOU

         TAKE A LOOK AT WHAT WE FOUND IN THIS PARTICULAR

12        SLIDE,  YOU SEE THAT THE RANGE OF RELATIVE RETENTION

13        TIMES FOR EACH OF  THESE THREE COMPOUNDS ARE VERY,

         VERY NEAR TO  EACH  OTHER,   WE ONLY HAD A RANGE  OF

         0,03 OF A RETENTION TIME UNIT FOR THE DIOCTYL

         PHTHALATE, WHEREAS IN  MATCHING THE SPECTRUM FOR

         THAT SAME COMPOUND  (RUN IN DIFFERENT LABORATORIES)
18
         THE RANGE OF  K,  THAT IS THE OVERALL QUALITY OF THE
19                                     _
         MATCH,  WAS A  FACTOR OF TWO,   THE SAME GOES FOR THE
20
         OTHER TWO COMPOUNDS SHOWN,   ONE CAN SEE  THERE'S A
21
         MUCH GREATER  RANGE IN  THE  MATCH PARAMETER THAN THERE  IS
22
         IN  THE  RELATIVE  RETENTION  TIME.   WE WERE MILDLY EXCITED
23
         ABOUT THIS,   WE  DIDN'T KNOW HOW WELL THE CORRELATION
24
         FROM LAB TO LAB  WOULD  BE,  BUT THIS GAVE  US A LITTLE
25
         BIT OF  ENCOURAGEMENT,
                                 127

-------
           SLIDE 15, PLEASE.  WE DETERMINED EMPIRICALLY  SOME
2       RELATIVE RETENTION TIME WINDOWS AND COLLECTED SOME
3       STATISTICS,  THE RELATIVE RETENTION TIME MATCHES
        FROM LAB TO LAB HAVE BEEN UNBELIEVABLY GOOD,  THE
5       REASON FOR THIS IS THAT SO MANY PEOPLE ARE USING
6       AUTOMATED GC/MS SYSTEMS THAT  REQUIRE THEM TO HAVE
7       GOOD PRECISION IN RELATIVE RETENTION TIMES TO
8       EFFICIENTLY ANALYZE THESE PRIORITY POLLUTANTS,
9       HERE is AN EXAMPLE OF TWO LABORATORIES WHOSE DATA
10       WAS OUTSIDE THE PRECISION WINDOW  FOR RELATIVE
11       RETENTION TIME, YET FELL VERY CLOSE TO EACH OTHER,
12       WE WERE ABLE TO APPLY A LINEAR CORRECTION FACTOR
13       THAT BROUGHT THESE  INTO LINE  WITH EVERYONE ELSE,
14       OUR WINDOW  FOR THE SP-2250 COLUMN IS ±,06 RELATIVE
15       RETENTION TIME UNITS,  As YOU CAN TELL, AFTER APPLY-
16       ING THE CORRECTION, THEY WERE BROUGHT WELL WITHIN
        THOSE  LIMITS,
18          SLIDE 16, PLEASE,  HERE ARE THE SAME TWO LABORA-
19       TORIES ON THE SP-1240-DA COLUMN,  AGAIN, WE WERE ABLE
20
        TO APPLY A  LINEAR CORRECTION  THAT BRINGS THEM  INTO
21       THE SAME RANGE AS ALL THE OTHER  LABORATORIES,
22          SLIDE 17,  AT THE OUTSET  IT WAS OBVIOUS THAT  THERE
23       WERE  GOING  TO BE PROBLEMS ASSOCIATED WITH COMPOUNDS
24       THAT  HAD VERY SIMILAR SPECTRA,  WE DECIDED TO  PROCURE
25
        A NUMBER OF HOMOLOGOUS  SERIES STANDARDS AND  GET  THEM
                                 128

-------
Table I.  Mean RRT's for   two  labs   ibefore and  after correction,

comoared with mean RRT's for other labs for 1% SP-2250.
                         RRT for   two labs
                         before        after   ^      RRT for all
Compound               correction    correction       other labs

Xylenes

2-N-Butoxyethanol

C_ Benzenes

Naphthalene

Methyl Naphthalenes

C2 Naphthalenes

Fluorene
.041
.090
.111
.3752
.491
.612
.7962
.137
.180
.200
.438
.542
.651
.816
.133
.166
.208
.457
.553
.663
.838
 corrected using following formula:

     RRTcorrected = RRTorig +  O'1  (1 '  RRTorig>    (for RRTorig<:L)

2
 one observation only
                                   128A

-------
Table II.   Mean RRT's for  two labs    before and after correction


compared with mean RRT's for other labs for 1% Sp-1240-DA.
                         RRT for   two labs

                         before        after   ^       RRT for all
Compound               correction    correction        other labs


Naphthalene               .180         .344               .343


Methyl Naphthalene        .280         .424               .453


Benzothiazole             .2933        .434               .4753


Phenol                    .322         .458               .4672


Cresols                   .371         .497               .489


C2 Naphthalenes           .383         .506               .542


Xylenols                  .466         .573               .589


C3 Naphthalenes           .524         .619               .661


Dibenzofuran              .612         .690               .719
 Corrected using following formula:

     "^corrected" RRTorig+  °'2  (1 ' RRTorig}     (for RRTorig<:L)


 2
 RRT from Protocol



 one observation only
                                   128B

-------
HOMOLOGOUS   SERIES   STANDARDS

                 C6 -  C19 N-ALKANES
                 C19 " C40 N-ALKANES
                  C6 - C1Q ALKENES
                  C8 - C22 ALKENES
                C4 - C22 N-ALCOHOLS
                 C3 -  C16 ALDEHYDES
              C4 - Cw PRIMARY AMINES
       C^ - C18 SECONDARY AND TERTIARY AMINES
               BENZENOID HYDROCARBONS
                 DICARBOXYLIC ACIDS
       DIMETHYL ESTERS OF DICARBOXYLIC ACIDS
                C3 - C18 FATTY ACIDS
                  C3 - C12 GLYCOLS
               C3 - C1Q GLYCOL ETHERS
                 LOW BOILING ESTERS
              C3 - Clg METHYL KETONES
                      PHENOLS
                  PHTHALATE ESTERS

-------
1          RUN ON THE GC/ffiS BY TWO LABORATORIES,  SlNCE WE KNEW
2          THAT WE WERE GETTING GOOD CONSISTENT RELATIVE RETEN-
3         TION TIMES, THESE WERE PUT IN OUR LIBRARY,  THE MAIN
4         SELECTION CRITERIA WERE THAT THEY WERE AVAILABLE AND
5         CONSTITUTED A PROBLEM AREA,
e            SLIDE 18,  THIS is AN EXAMPLE OF THE WAY THINGS
7         CAN WORK (IN THE BEST CASE, OF COURSE),  As YOU SEE
8         HERE, WE HAVE MANAGED TO IDENTIFY A LARGE NUMBER OF
9         COMPOUNDS  IN AN ACID FRACTION,
10            SLIDE 19, PLEASE.  HERE ARE SOME SELECTED RESULTS
11         FROM OUR HISTORICAL LIBRARY,  REMEMBER, OF COURSE,
12         THAT ALL OF THESE COMPOUNDS ARE TENTATIVE AND HAVE
13         NOT BEEN CONFIRMED CHEMICALLY,  ALL THAT THIS SLIDE
14         DEMONSTRATES IS THAT SOME CHEMICALS SHOW UP IN SOME
15         INDUSTRIES SELECTIVELY,
16            SLIDE 20,  As I SAID BEFORE, WE'RE TAKING SPECTRA
17         THAT DO NOT MATCH WITH THE REFERENCE LIBRARY, MATCH-
18         ING THESE  AGAINST EACH OTHER TO SELECTIVELY PRIORITIZE
19         THOSE THAT REOCCUR,  NEXT, THE EXTRACT, CORRESPONDING
20         TO A SAMPLE IN WHICH THIS COMPOUND WAS FOUND IN HIGH
21         CONCENTRATION, I S ANALYZED TO IDENTIFY THI S COMPONENT BY
22         USING MORE  EXTENSIVE METHODS OF ANALYSIS,  THIS PROJECT
23         IS UNDERWAY NOW VIA A CONTRACT BETWEEN THE ATHENS
24         LABORATORY AND RESEARCH TRIANGLE INSTITUTE,  AT
25         THE PRESENT TIME, RTI IS ANALYZING EXTRACTS THAT
                                 129

-------
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-------
SELECTED    HISLIR   RESULTS



COMPOUND
BENZALDEHYDE
DIMETHYLSULFONE
X-PINENE
£-PINENE
TRIBUTYLPHOSPHATE

TOTAL
HISLIB
ENTRIES
7
3
9
9
10
% OF ENTRIES
FOUND IN
INDICATED
INDUSTRY
71%
100%
66%
39%
50%
BORNEOL                         10


2,4-DIHYDROXYACETOPHENONE       7
DIPHENYLETHER                    5
BENZOTHIAZOLE                    4
TETRAHYDROFURAN                  5
2-ETHYL-l-HEXANOL              25
2-METHYLANTHRACENE             13
1&3&9 METHYLPHENANTHRENE       1L\
DIBENZOFURAN                     3
PYRENE                          6
                                       70%
                                       36%
                                       75%
                                       100%
                                       63%
                                        75%
                                        67%
  INDUSTRY
PULP S PAPER
PULP & PAPER
PULP & PAPER
PULP & PAPER
PULP 8 PAPER
PAINT &  INK
PULP & PAPER
PAINT S  INK
PULP S PAPER
ORGANics  ft PLASTICS
RUBBER PROCESSING
TEXTILE  MILLS
PAINT &  INK
COAL fliNiNG
COAL MINING
COAL MINING
COAL MINING
                             129B

-------
    PROGRAM FOR IDENTIFICATION OF UNKNOWNS


A,   UNKNOWNS WITHIN A GIVEN RETENTION TIME WINDOW
        ARE MATCHED AGAINST EACH OTHER TO DETERMINE
        FREQUENCY OF OCCURRENCE,

B,   THOSE UNKNOWNS WITH THE HIGHEST FREQUENCIES OF
        OCCURRENCE AND RELATIVE CONCENTRATIONS ARE
        DESIGNATED FOR FURTHER STUDY UNDER TASK 160,
                      129C

-------
1        CONTAIN SOME OF OUR TENTATIVELY  IDENTIFIED COMPOUNDS
2        TO BE CONFIRMED BY COINJECTION WITH A STANDARD.
3          SLIDE 21,  ONE OF THE BIG  PROBLEMS WE HAVE HAD
4       IS TRYING TO DETERMINE THE  INTERNAL STANDARD  IN MANY
5       OF THESE RUNS,  FlANY TIMES  IT'S  BY FAR THE SMALLEST
6       COMPONENT OF THE RUN AND BURIED  IN THE BACKGROUND,
7       WE WANTED TO DO SOMETHING TO  HELP US FIND THIS
8       COMPONENT BY LOOKING AT THE SPECIFIC ION PLOTS
9       FOR CHARACTERISTIC  IONS OF  THE  INTERNAL STANDARD,
10       THIS  IS AN  EXAMPLE OF HOW THE BACKGROUND SUBTRACT
11       MODULE LOOKS,
12          AT THE TOP OF THE SLIDE  YOU'LL SEE MASS 55 AS
13       IT'S  SEEN IN THE RAW DATA,  ON  THE BOTTOM, IT  IS MASS
14       55 AFTER THE BACKGROUND SUBTRACT IS DONE.  THE  PROGRAM
15       ACTUALLY HELPS THE  PEAK FINDING ALGORITHM BY  MAKING
16       THE PEAKS THAT ARE  ACTUALLY THERE STAND OUT,  AFTER
17       WE HAD DONE THIS, WE FOUND  WE COULD PUT  IT TO SOME
18       OTHER USES  SUCH AS  REVERSE  SEARCHING AS  IS DONE IN
19       PRIORITY POLLUTANT  ANALYSIS,  WE WERE ASKED TO
20       LOOK  AT SOME  PAINT  AND  INK  EFFLUENT SAMPLES TO  SEE
21        IF WE COULD FIND  SOME  CHLORINATED BIPHENYLS,   OUR
22       PROGRAM PEAK,  THE  INTERNAL  STANDARD  FINDER, WAS
23       ADAPTED TO  USE MASSES  CHARACTERISTIC OF  SEVERAL
24        PCBS  INSTEAD  OF  THE MASSES  OF THE  INTERNAL  STANDARD,
25       WE  DID NOT  FIND  ANY PCBs,  BUT WE DID  FIND  SOME
                                JJiO_

-------
  100 n
    0
       FILE: DBO:C203,2033651-DflT
       T/D  08:37  ll-SEP-79    MflSS >  55
                                               RflW  INT.
                                               RT SPEC.
 2946
 350
 RI  -4
200   220   240   260   280   300   320   340
                              M/Z
                                                   360   380   400
      FILE:  DBO:C203,2033651.BCK
      T/D   08:37   ll-SEP-79     MflSS  >  55
                                              RflW  INT.
                                              flT SPEC.
 1952
 260
 100 -i
RI  H
   0
    200
                                                  360
                                                  380
400

-------
1        CHLORINATED AROMATICS THAT MATCHED ONE OR MORE OF
2
5
        THE PCB MASSES WE WERE LOOKING FOR,
3          THE IMPORTANT PART HERE  IS THE  FACT THAT WE HAD
        SOME 20,000 SPECTRA TO GO THROUGH  TO  FIND THESE
        PCBS, AND THIS ALGORITHM ALLOWED  US TO  REDUCE THE
6       DATA DOWN TO ONLY 34 SPECTRA OF  INTEREST,
7          SLIDE 22  is AN EXAMPLE  OF ONE  OF  THE  SPECTRA
8       THAT WE FOUND  IN THAT  PARTICULAR  RUN AND YOU  CAN
9       SEE THE CHLORINE PATTERN EASILY,
10          AS  I HAVE SAID,  I HAVE  SHOWN  YOU  THE  BEST  OF OUR
11       DATA,  AS YOU  CAN  IMAGINE,  THE TYPE  OF DATA IN  SLIDE
12       23 DOESN'T WORK TOO WELL SOMETIMES,  AND  THIS  is REALLY
13       NOT THE WORST  OF  IT,   As YOU WHO HAVE RUN SOME  OF
14       THESE  SAMPLES  KNOW, WE GET HUMPOGRAMS MANY TIMES
15       THE COMPUTER PROGRAM  JUST  CAN'T  HANDLE THIS,  SO
16       WE'RE  ENDEAVORING  TO  IMPROVE THE SYSTEM,  I CAN
17        ENTERTAIN  QUESTIONS AT THIS TIME IF  THERE ARE ANY,
18
19
20
21
22
23
24
25
                                  131

-------
                 CHLORINATED ORGANIC FOUND WHEN REVERSE SEARCH EMPLOYED
SPEC 513/150,SSO
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-------
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-------
132

-------
                        QUESTION  AND  ANSWER

1                              SESSION



                                 MR, SPRAGGINS:  WALT, THIS
3

        IS REAL INTERESTING DATA,  I'M VERY  INTERESTED IN
4

        THIS SORT OF PROGRAM,  HAVE  YOU GOT  ANY DATA YET,
5

        OR HOW LONG WILL  IT BE BEFORE YOU  HAVE DATA ON
6

        CONCENTRATION?


                                 MR, SHACKELFORD:  WELL, AS
8

        YOU CAN IMAGINE OUR CONCENTRATIONS ARE REALLY MEAN-
9

        INGLESS,  FOR WE KNOW  NONE OF THE RESPONSE  FACTORS,
10

        I HATE THE  FACT THAT  THE COMPUTER  PRINTS OUT NUMBERS,
11

        I WISH IT WOULD ONLY  PRINT BIG AND LITTLE, BUT THAT'S
12
        REALLY ABOUT ALL  WE'RE WILLING TO  SAY ON CONCENTRA-
13

        TION,  IN OTHER WORDS, WE ASSUME THAT Din  ANTHRACENE
14                                              1U

        AND ALL OF  THE  COMPOUNDS WE  LOOKED AT HAVE THE SAME
15
        RESPONSE  FACTOR  (OF COURSE,  THAT'S FOOLISHNESS), BUT
16

        THAT'S REALLY THE ONLY WAY WE CAN  GET SOME INDICATION,


                                 MR, SPRAGGINS:  ARE YOU TRY-
IS

        ING TO PLOT THE DATA  OUT THAT GIVES  YOU AN IDEA OF
19

        WHAT THE  COMPOUND IDENTIFICATIONS  LOOK LIKE VERSUS
20

        CONCENTRATION FOR A GIVEN  INDUSTRY OVER A  SERIES OF
21

        INDUSTRIES, THE NUMBER OF TIMES YOU  ACTUALLY  FIND A
22

        COMPOUND  WITHIN AN INDUSTRY? HAVE YOU GOT ANY PLOTS
23

        LIKE THIS?

                                 MR, SHACKELFORD:  WE  HAVE
25
                                133

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NOT DONE ANY PLOTS AT THE PRESENT TIME.  THAT  SLIDE
I SHOWED, SLIDE 19, SHOWS SOME OF THE COMPOUNDS
THAT WERE SHOWING UP IN SOME INDUSTRIES,  WE PREFER
TO WAIT UNTIL WE GET SOME OF OUR DATA BACK FROM THE
CONFIRMATION STUDY BEFORE WE ATTEMPT TO CHARACTERIZE
AN INDUSTRY,  FOR INSTANCE, DREW SAUTER WHO IS WORKING
WITH THE LAS VEGAS LAB NOW, is ONE OF THE PEOPLE WHO
DESERVES PRINCIPAL CREDIT FOR THIS WORK,  HE HAS PUT
FORTH SEVERAL VERY GOOD IDEAS THAT WE ARE GOING TO
PURSUE TOWARD A PATTERN RECOGNITION TYPE OF STUDY ON
THE COMPOUNDS FOUND IN VARIOUS INDUSTRIES,
                         MR, TELLIARD:  THE NEXT
SPEAKERS ARE GOING TO TALK ABOUT THE PRECISION AND
ACCURACY STUDIES THAT WE HAD INITIATED LAST MEETING,
WE'VE DONE SOMETHING LIKE 14 INDUSTRIES,  BASICALLY,
WHAT HAS HAPPENED IS WE WERE GOING TO BLIND YOU WITH
DATA AND ALL THAT GOOD STUFF; HOWEVER, MY CONTRACTOR
WAS BUSY HAMMERING OLD CHEMICAL DATA FROM THE MANUFAC-
TURING CHEMISTS' GROUP, AGAIN, FOR TWO YEARS, so
GEORGE CAN MAKE YOU SLIDE, so THEY NEVER GOT TO MY
DATA,  WE'RE GOING TO GIVE YOU A GENERAL OVERVIEW
FROM HIKE CARTER AND ALSO BOB BEIMER FROM TRW, WHO
IS WORKING ON A LITTLE DIFFERENT PART OF THE STUDY,
WHICH IS WHAT WE'RE CALLING A SOLIDS STUDY OR
SUSPENDED SOLIDS STUDY,
                          134

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 1                  PRECISION AND ACCURACY STUDIES
 2
 3                         BY:  MIKE CARTER
 4 |           AS BILL MENTIONED, THERE  IS A PRECISION AND
  i
 5       ACCURACY STUDY GOING ON DESIGNED TO LOOK AT APPROXI-
 6 !      MATELY 28 INDUSTRIAL SAMPLES THAT WILL PRETTY MUCH
 7 !      COVER THE RANGE OF INDUSTRIAL  CATEGORIES,  SOME OF
 8 •      THEM, APPARENTLY, WE NEED TO LOOK AT MORE THAN ONCE,
 9 !      IN AT LEAST ONE CASE, WE'VE REPEATED AN  INDUSTRY
10 I      BECAUSE THE DATA JUST WAS NOT  TOO GOOD,  WE GOT A
        LOT BETTER RESULTS THE SECOND TIME AROUND,  SlNCE
        WE'RE ONLY ABOUT HALFWAY THROUGH, WE HAVEN'T GOTT
        ALL THE DATA PLUGGED INTO A DATA BASE YET,  UNTIL
13
14      THEN, NO STATISTICAL WORK CAN BE DONE ON IT, SO WE'RE
15 |     JUST NOT GOING TO BE IN A POSITION TO GIVE ANY NUMBERS
16 I     SUCH AS BOB KLEOBFER DID,
17 j          IN GENERAL, IT'S MY IMPRESSION THAT THE RECOVERIES
18      AND STANDARD DEVIATIONS ARE COMPARABLE TO WHAT B-OB
19      HAS SHOWED YOU,  THE STUDY DOES LOOK AT BOTH
20 j     INFLUENT TO TREATMENT AND EFFLUENT FROM TREATMENT,
21       THERE ARE DUPLICATES RUN AT FIVE DIFFERENT CONCEN-
22      TRATIONS IN EACH TYPE OF SAMPLE.  nNE OF THE
23      CONCENTRATIONS IS A NONSPIKED LEVEL,   THE SPIKE
24      LEVELS ARE NOT BASED ON THE CONTENT OF THE SAMPLE;
25       IT'S MORE BASED  ON  THE INDICATED CONCENTRATIONS
                                  135

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 1       FROM SCREENING THAT OCCURRED  IN THAT  INDUSTRY,   So
 2       WE ATTEMPT TO MAKE FOUR SPIKES THAT WILL  FAIRLY  WELL
 3       BRACKET THE CONCENTRATIONS THAT WERE  INDICATED BY
 4       THE OUTPUT FROM THE SCREENING QUANTITATION,   ONE
 5       BIT OF INFORMATION THAT IS COMING OUT A LOT  IS THAT
 6       THE EFFLUENT FROM TREATMENT IS A LOT  EASIER  MATRIX
 7       TO WORK WITH THAN THE INFLUENT TO TREATMENT,  AND
 8       THAT'S NOT REALLY SURPRISING,
 9            OF THE STUDIES THAT WE HAVE TO DATE, THE
10       TIMBER INDUSTRY GIVES A STRIKING CONTRAST BETWEEN
11       THE TWO MATRICES,  I AM TALKING ABOUT STANDARD
12       DEVIATIONS IN GENERAL; IN THE BASE/NEUTRAL,  AS
13       HIGH AS 200 PERCENT RECOVERY, WHEREAS IN THE
14       EFFLUENT, THE STANDARD DEVIATION DROPS DOWN  TO THE
15       RANGE OF 15 TO 20,  IT'S A VERY DRAMATIC DEMONSTRATION
16       OF THE EFFECT OF MATRIX,
17            ONE ASPECT THAT IS BEING LOOKED AT IN THE
18       PRECISION AND ACCURACY STUDY  IS WHAT WE ARE  REFERRING
19       TO AS CROSSOVER.  BY THAT, WE MEAN THAT AFTER A
20       FRACTIONATION IS PERFORMED, ACCORDING TO THE  PROTOCOL,
21       THE ACID FRACTION IS ANALYZED BY GC/MASS  SPEC FOR THE
22       PRESENCE OF BASE/NEUTRALS AND VICE VERSA,  BOB KLEOBFER
23       MENTIONED THAT THE PHTHALATES TEND TO BE  VERY
24       TROUBLESOME,  PART OF THIS PROBLEM, I THINK,  IS  DUE
25       TO THE FACT THAT A LOT OF THE PHTHALATES  DO  NOT  COME
                                  136

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 1       OUT WHOLLY IN THE BASE/NEUTRAL FRACTION,  A SIGNIFI-



 2       CANT CONCENTRATION OF SOME OF THEM END UP IN THE



 3       ACID FRACTION,  So THE FACT THAT YOU'RE NOT LOOKING



 4       AT ALL THE PHTHALATE IN ONE ANALYSIS COULD VERY WELL



 5       EXPLAIN A LOT OF THE SCATTER,  THIS CROSSOVER



 6       APPEARS TO BE MATRIX DEPENDENT BECAUSE IT IS NOT



 7       CONSISTENT FROM INDUSTRY TO  INDUSTRY,  THE PHTHALATES



 8       AND THE PHENOLICS ARE THE MOST TROUBLESOME OF THE



 9       PRIORITY POLLUTANTS IN THE CROSSOVER STUDY,



10            THE STUDY THAT BOB BEIMER is GOING TO TALK ABOUT



11       ADDRESSES THE EFFECT OF TOTAL SUSPENDED SOLIDS,  To



12       DATE WE HAVE HAD FOUR SAMPLING EPISODES OR STUDIES



13       THAT WERE DONE BY BOTH TRW AND CARBORUNDUM,  |t(E



14       HAVE NOT DONE ANY COMPARISON BETWEEN THE TWO



15       LABORATORIES YET,  THAT, OF COURSE, WILL BE A VERY



16       REASONABLE THING TO DO,  WE SHOULD BE ABLE TO PRESENT



17       STATISTICAL DATA SHOWING AVERAGE RECOVERIES AND



18       STANDARD DEVIATIONS ON THESE STUDIES AT A LATER DATE,



19            I'LL ENTERTAIN ANY QUESTIONS BEFORE BOB STEPS



20       UP HEREj  IF  I CAN ANSWER A QUESTION, I'LL BE GLAD TO,



21



22



23



24



25
                                1ZL

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138

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                         QUESTION AND  ANSWER
                             SESSION
1                                 MR, GATES:  LARRY GATES
2       WITH  RADIAN,   How SIGNIFICANT,  YOU KNOW, ROUGHLY,
3       JUST  A BALLPARK,  WHAT RANGES DO YOU FIND THE
4       CROSSOVER  IN  TERMS  OF PERCENT FROM,LIKE, THE PHENOLS
5       AND THE PHTHALATES, OR  ARE  WE TALKING  ABOUT MAYBE
6       A  TEN PERCENT OF  A  GIVEN PHENOL BEING  IN THE BASE
7       NEUTRAL FRACTION  OR WHAT KIND OF RANGE?
8                                MR, CARTER:   IN AN EXTREME
9       CASE,  AND I'M  TALKING ABOUT  AN INFLUENT TO TREATMENT
10       THAT'S A VERY BAD MATRIX, THE INDICATED RECOVERY CAN
11       BE OVER 100 PERCENT OF  PHTHALATE SHOWING UP IN THE
12       ACID  FRACTION,  THIS IS NOT  A GENERALIZED STATEMENT;
13       THIS  IS REALLY AN OUTLIER-TYPE  EVENT,  BUT IT WOULD
14       BE SOMETHING  THAT COULD HAPPEN  ON  AN INDIVIDUAL
15       DETERMINATION,
16                               r1R,  GATES:  THEN FOLLOWING
17       FROM  THAT, THEN,  SINCE  IT IS MATRIX DEPENDENT,  THE
18       CROSSOVER  EFFECT, WOULD YOU  GUESS  THAT YOU  OBSERVE
19       CROSSOVER  OF  PHTHALATES AND  PHENOLS IN,MAYBE,WHAT
20       PERCENTAGE OF  THE EXTRACTS?   MAYBE  5,  10 PERCENT,  50
21       PERCENT?   I'M  TRYING  TO GET  SOME FEEL  FOR THE
22       SIGNIFICANCE  OF THE  PROBLEM,
23                               MR,  CARTER: I  REALLY  CAN'T
24       GIVE  YOU A GOOD ESTIMATE OF  THAT NUMBER,  WE'RE ONLY
25       HALFWAY THROUGH THE  STUDY,   MOST OF THE TIME  YOU DON'T
                                139

-------
 1       GET A CROSSOVER OF MORE THAN—AND  I'M  JUST TRYING
 2       TO RECALL THE NUMBERS—MORE THAN MAYBE 30,  40
 3       PERCENT IN MOST CASES,
 4                                W..  KEEN:   GARY  KEEN,
 5       CONTINENTAL OIL.   I HAVE OBSERVED  CROSSOVER WITH
 6       PHTHALATES BECAUSE OF HALF-ESTERS  THAT WILL BE
 7       EXTRACTED BECAUSE  THEY ARE REALLY  AN ACIDj  THEY
 8       THEN DISPROPORTIONATE IN THE  INJECTOR  TO  GIVE
 9       PHTHALIC ANHYDRIDE AND THE DIESTER,
10                                .MR,  CARTER:   THANK YOU,
n                                MR,  MPRS:  DAVE MARRS,
12       STANDARD OIL.  ONE QUESTION REGARDING  THE SPIKING,
13       WHAT SPIKING LEVELS DID YOU CHOOSE?  You  MENTIONED
14       FIVE LEVELS; DID YOU HAVE ANY BALLPARK KIND OF
15       FIGURES?
is                                MR,  CARTER:   WELL,  AS I
17       MENTIONED, ONE SPIKE LEVEL IS NOT  REALLY  A SPIKE
18       LEVEL,  IT IS JUST  THE AMBIENT SAMPLE SO WE'LL HAVE
19       SOMETHING TO BASE  THE SPIKE RECOVERY ON,   THE OTHER
20       SPIKE LEVELS WERE  BASED ON THE  REPORTED CONCENTRA-
21       TIONS FROM THAT INDUSTRY,  IN GENERAL, IT WAS,
22       FOR THE INFLUENT TO TREATMENT,  SOMETHING  LIKE 50,
23       200, 500, 750,  IN THE EFFLUENT FROM TREATMENT,  IT
24       WOULD BE 20 TO 50, 100, 250,  500,   As  I SAID, WE
25

-------
1       TRIED  TO  BRACKET WHAT HAD ACTUALLY BEEN REPORTED,
2                                 MR.  MAPRS:  IN CHOOSING
3       YOUR  LEVELS FOR SOME OF THE PARTICULARLY INSOLUBLE
4       SOLUBLE COMPOUNDS,  DID YOU GIVE SOME THOUGHT TO THE
5       SOLUBILITY LIMIT, SAY, OF A PAH OR SOMETHING LIKE
6       THAT  AND MAKE THAT YOUR UPPER LIMIT IN CHOOSING
7       YOUR  SPIKING LEVEL?
8                                MR,  CARTER:   IN GENERAL,
9       YES,  WE TRIED TO DO THAT, AT THE SAME  TIME, TRYING
10       TO ADDRESS ANY REPORTED VERY HIGH  FIGURES,
u                                MR,  M.ARRS:  WHAT SOLVENT
12       DID YOU USE FOR  YOUR  SPIKING?
13                                MR,  CARTER:   METHYLENE
14       CHLORIDE FOR EXTRACTABLES AND METHANOL  FOR PURGEABLES,
15                                DR, COLBY:  BRUCE  COLBY,
16       SYSTEMS,  SCIENCE AND  SOFTWARE,  VHEN THE  EXTRACTIONS
17       ARE BEING  DONE,  IS  THERE A PRECAUTION  TAKEN TO
18       ASSURE THAT THE  PH  IS NOT  CHANGING AS  A FUNCTION  OF
19       TIME?  I  MEAN,  IF WE  SET  UP  AN  EXTRACTION AND  EITHER
20       SHAKE IT  OR WAIT FOR  IT  TO GO THROUGH  A CONTINUOUS
21       EXTRACTION, OCCASIONALLY  THE P'H WILL  ACTUALLY  CHANGE
22       DURING THE PROCESS,   Is  THAT BEING CHECKED  FOR?
23                                 MR, TELLIAPD: YES,  WE
24       MEASURE  PH, WE MEASURED  PH AFTER  EACH EXTRACTION
25       BEFORE  DISCARDING  AND AFTER  EACH  EXTRACTION,
                                  JAL

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                                 MR,  HENDERSON:   JIM HENDERSON
 2       WITH CARBORUNDUM,  JUST TO  FOLLOW  UP  ON  YOUR
 3       QUESTION A LITTLE BIT, BRUCE,  I DO  KNOW  THAT IN
 4  j     ONE SET OF SAMPLES, FOR SURE,  THEY  WERE  MADE BASIC
 5       AT THE BEGINNING OF THE RUN AND THEY  WERE NOT BASIC
 6  !     AFTER THE 24-HOUR PERIOD, AND  AFTER THAT PHENOMENON
   I
 7  !     OCCURRED, WE BEGAN TO MEASURE  PHS BEFORE THE EXTRAC-
 8       TION STARTED, AFTER THE BASIC  EXTRACTION,  AFTER THE
 9  j     ACID EXTRACTION,
10                                MR, CARTER:  ONE OTHER
11  |     THING THAT IS BEING DONE IN THE PRECISION AND ACCURACY
12       STUDY IS THAT SURROGATE SPIKES SUCH AS BOB I
-------
        CHEMICAL-RUBBER HANDBOOK WOULD NOT BE  EXCEEDED,
2 i      THERE HAVE BEEN NO REAL STUDIES DESIGNED  TO  ASSESS
3       THAT SOLUBILITY, BUT WE DID  REFER TO THE  LITERATURE
4       FOR THE SOLUBILITY OF  METHYLENE CHLORIDE,
5 |                               MR,  RHOADES:   JOHN  RHOADES
e |      WITH SOUTHWEST RESEARCH INSTITUTE.   WE  FOUND  THAT IF
7 |      YOU GET REAL BASIC,  IF YOU GET DOWN TO PH12  OR SO,
8 |      YOU'LL  GET PRACTICALLY NO  DIMETHYL BACK.;  YOU'VE GOT
9 I      TO STAY UP AROUND 10 OR SO,   To SOME EXTENT THE SAME
10 I      THING AS  WITH THE DIETHYL.
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
                                  JL41

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144

-------
 i                  PRECISION AND ACCURACY STUDIES
 2                      BY:  ROBERT G, BEIMER
 3            I WANT TO START OFF BY SAYING THAT I PREPARED
 4       THE SLIDE MATERIAL THAT I'M GOING TO PRESENT HERE,
 5       BUT I EXPECTED BlLL TELLIARD TO PRESENT THIS,   IF
 6       I HAD KNOWN I WAS GOING TO PRESENT IT, I'D HAVE DONE
 7       A BETTER JOB OF PUTTING THE SLIDES TOGETHER.
 8            I WANT TO TALK BRIEFLY, AND I DO MEAN BRIEFLY,
 9       ABOUT SOME OF THE WORK WE'RE DOING ON THE PRECISION
10       AND ACCURACY STUDY,  I'M NOT GOING TO GO  INTO ANY
11       OH THE ACTUAL ANALYSES THAT WE PERFORMED AND THE
12       RECOVERY OF THE PRIORITY POLLUTANTS BECAUSE THAT
13       DATA REALLY HASN'T ALL BEEN PUT TOGETHER TO A
14       POINT WHERE IT CAN MAKE A LOT OF SENSE.   I WANT TO
15       ADDRESS INITIALLY THE CROSSOVER PROBLEM AND SHOW
16       SOME DATA WE HAVE GENERATED WHICH ILLUSTRATES
17       THE CROSSOVER PROBLEM,  THE LAST STATEMENT THAT
18       WAS MADE HERE ABOUT NOT GOING TO A HIGH Pf! FOR
19       THE BASE/NEUTRAL FRACTION REALLY LEADS INTO THIS,
20       THE MAJORITY OF WHAT I'VE GOT HERE,,.WELL, EXCUSE
21       ME, ALL OF WHAT I'VE GOT HERE IS RELATED  TO SURROGATE
22       SPECIES RATHER THAN PRIORITY POLLUTANT SPECIES,  NOW,
23       THE REASON THAT I'M SHOWING;'SURROGATE COMPOUNDS  IS
24       BECAUSE THESE MATERIALS WERE ALL SPIKED AT THE  SAME
25
                                 145

-------
 1       LEVEL IN  ALL OF THE SAMPLES,  MlKE CARTER SAID THAT




 2       THERE WERE  FIVE SPIKING LEVELS FOR THE PRIORITY




 3       POLLUTANTS,  AND THAT'S TRUE,  BUT IN EACH ONE OF THOSE




 4       SAMPLES WE  SPIKED THE SURROGATES AT 100 MICROGRAMS




 5       PER  LITER,  CONSTANT,  THROUGHOUT, So ALTHOUGH THERE




 6       WAS  A SLIGHTLY  DIFFERENT MATRIX BECAUSE OF THE



 7       VARYING SPIKING LEVELS OF THE PRIORITY POLLUTANTS, THE



 8       SURROGATE MATERIALS THEMSELVES WERE CONSTANT,




 9         NOW, I'M  GOING TO  TELL YOU WHAT'S ON HERE BECAUSE



10       I  DOUBT THAT YOU CAN  SEE THIS VERY WELL.



n       THE  FOUR  INDUSTRIAL CATEGORIES THAT ARE PRESENTED



12       ON THIS SLIDE ARE NONFERROUS  METALS, INORGANIC



13       CHEMICALS,   PUBLICLY  OWNED TREATMENT WORKS,  AND



14       THE  TEXTILE  INDUSTRIES,  ALL OF THESE SAMPLES WERE




15       EXTRACTED USING METHYLENE CHLORIDE IN 24-HOUR



16       CONTINUOUS  LIQUID/LIQUID EXTRACTORS, THE




17       FIRST THREE  INDUSTRIES WERE EXTRACTED AT  AN  INITIAL



18       PH.OF 11, MEASURED WITH A PH  METER BEFORE AND  AFTER




19       EXTRACTION,  AND THE FINAL CATEGORY,  THE TEXTILE



20       INDUSTRY, WAS EXTRACTED INITIALLY AT A PH OF 12.




21         NOW,  IF YOU LOOK AT THE RECOVERIES, WHAT IS  PRESENTED



22       HERE IS THE  PERCENTAGE OF THE VARIOUS SURROGATE



23       MATERIALS FOUND IN EACH FRACTION,  NOW, IF YOU  LOOK AT



24



25
                                146

-------
 1       THE FIRST ONE, 2-FLUOROPHENOL.   IN  THE ACID
 2       FRACTION FOR THE NONFERROUS METALS  CATEGORY,  FOR
 3       INSTANCE, 70 PERCENT WAS  FOUND  IN THE ACID FRACTION
 4       AND 30 PERCENT IN THE BASE/NEUTRAL  FRACTION,  GOING
 5       ACROSS TO DCJ PHENOL, WHICH  IS LESS  OF AN ACID THAN
 6       2-FLUOROPHENOL, ONLY 11 PERCENT  OF  THE DC; PHENOL WAS
 7       FOUND IN THE ACID FRACTION, WITH 89 PERCENT FOUND  IN
 8       THE BASE/NEUTRAL FRACTION,  NOW, DC; PHENOL IS A LOT
 9       LIKE PHENOL, SO IF YOU'RE DOING  YOUR EXTRACTION AT A
10       PH OF 10 OR 11, MOST OF YOUR PHENOL IS IN THE BASE/
11       NEUTRAL SIDE, AND IF YOU'RE NOT  ANALYZING THE BASE/
12       NEUTRAL FRACTION FOR THE  PHENOLS, YOU'RE MISSING THEM,
13            IF YOU GO DOWN TO THE BOTTOM LINE, NOW, THE
14       TEXTILE INDUSTRY EXTRACTED AT A  PH  OF 1?.  y/IRTUALLY
15       ALL OF THE MATERIAL WAS FOUND IN THE FRACTION WHERE
16       IT BELONGED; ROUGHLY 100  PERCENT—IT'S 98 PERCENT  IN
17       SOME CASES—WAS COUND IN  THE ACID FACTION,  So THIS
18       CROSSOVER, IF YOU WANT TO REFER  TO  IT THAT WAY, VARIES
19       SLIGHTLY WITH THE INDUSTRIAL CATEGORY, WHICH SAYS
20       THAT IT'S PROBABLY VARYING SOMEWHAT IN TERMS OF THE
21       MATRIX, BUT MORE SPECIFICALLY,  IT FOLLOWS THE
22       OF THE MOLECULES THAT WE'RE LOOKING AT ON THAT
23       CHART,   IN SHORT,  THE BETTER THE ACID, THE MORE
24       IT'S FOUND IN THE ACID FRACTION, AND THE POORER
25       THE  ACID,  THE LOWER  THE  PK  IT'S  FOUND  IN  THE
                                   147

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 1       BASE/NEUTRAL FRACTION,   So  YOU'VE GOT TO FORCE
 2       THE SITUATION,  ESPECIALLY USING CONTINUOUS EXTRACTORS,
 3       YOU'VE GOT TO FORCE THE SITUATION  SO THAT YOU DON'T
 4       ALLOW A SIGNIFICANT AMOUNT OF THE  PHENOL TO BE
 5       EXTRACTED IN THE BASE NEUTRAL FRACTION WHEN YOU'RE
 6       NOT ANALYZING THAT FRACTION FOR THE PHENOLIC COMPOUNDS,
 7       OBSERVATION NUMBER ONE,
 8         NOW, WE CAN COME BACK TO THAT IF ANYBODY HAS ANY
 9       QUESTIONS ON IT, BUT I WANT TO TALK NOW ABOUT THE SECOND
10       PART OF THE STUDY THAT WE ARE DOING, AND THAT IS THE
11       EFFECT OF TOTAL SUSPENDED SOLIDS ON PRIORITY POLLUTANT
12       RECOVERY,  NOW, AGAIN, WHEN WE STARTED PUTTING THIS
13       MATERIAL TOGETHER, WE LOOKED AT ALL THE PRIORITY
14       POLLUTANTS AND THEN WE THOUGHT, YOU KNOW, WE'RE TRYING
15       TO AVERAGE TOGETHER APPLES AND ORANGES WHEN WE'RE
16       TAKING AVERAGES OF SPIKING LEVELS  AT 20, AND SPIKING
17       LEVELS AT 2,000 AND TRYING TO MEASURE THE EFFECT OF THE
18       TOTAL SUSPENDED SOLIDS ON THOSE PRIORITY POLLUTANTS,
19       THEREFORE, AGAIN, WE WENT BACK TO  THE SURROGATE
20       MATERIALS THAT WE WERE SPIKING, ALL SPIKED AT THE SAME
21       CONCENTRATION,  AND USED THOSE TO TRY TO ESTABLISH THE
22       EFFECT OF SOLIDS ON PRIORITY POLLUTANT RECOVERY, $0 WHAT
23       I'LL SHOW YOU is THE EFFECT OF SOLIDS ON SURROGATE
24       MATERIAL RECOVERY AND YOU CAN TRANSLATE THAT TO PRIORITY
25       POLLUTANT RECOVERY IF YOU WISH; I  HODE THAT BEFORE  TOO
                                   148

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1        LONG,  AS  WE  GET MORE INDUSTRIAL CATEGORIES DEVELOPED,



2       WE  CAN HAVE  ENOUGH DATA THAT WE CAN TALK ABOUT THIS



3       KIND OF INFORMATION ON PRIORITY POLLUTANTS



4       DIRECTLY, BUT AT THIS POINT, ,ALL WE CAN TALK ABOUT



5       ARE THE SURROGATES,



6            THE  MOST CONFUSING THING ABOUT THIS WHOLE THING



7       IS  EXPLAINING WHAT WE DID,  IN THIS STUDY, WE WERE



8       DOING THE STANDARD PR.IORITY POLLUTANT ANALYSIS FOR



9       ORGANIC COMPOUNDS BY TAKING A REPRESENTATIVE AMOUNT



10       OF  THE SOLIDS AND THE LIQUID AND EXTRACTING IT IN



11       A CONTINUOUS EXTRACTOR; ANALYSIS NUMBER ONE, THE



12       NORMAL ANALYSIS,  ANALYSIS NUMBER TWO, WE SPIKED



13       THE MATERIAL INTO THE WATER, ALLOWED  IT TO  INCUBATE



14       FOR EIGHT HOURS, AND THEN FILTERED THE SOLUTION AND



15       PROCEEDED TO PERFORM PRIORITY POLLUTANT ANALYSIS,



16       IN THE THIRD CASE, WE FILTERED THE WATER AND THEN



17       SPIKED IT WITH THE PRIORITY  POLLUTANTS AND WENT



18       AHEAD WITH THE ANALYSIS,



19            NOW, WHAT THIS CHART REPRESENTS FOR THE NONFERROUS



20       METALS INDUSTRIAL  CATEGORY  IN THE FIRST COLUMN,



21       COLUMN A, IS THE RATIO  OF THE RECOVERY SPIKED BEFORE



22       FILTERING DIVIDED  BY THE  RECOVERY SPIKED AFTER



23       FILTERING,  WHAT THIS MEANS  is, AS THE NUMBERS



24       APPROACH ONE, THERE  IS  NO SOLIDS EFFECT ON  THE



25
                                  149

-------
 1       RECOVERY,  THE SMALLER THE  NUMBER,  THE GREATER



 2       THE EFFECT OF SOLIDS ON RECOVERY,   THE FIRST



 3       SIX COMPOUNDS UP THERE ARE  BASE/NEUTRAL SURROGATE



 4       MATERIALS,  THE LAST FOUR ARE  ACID  SURROGATE



 5       MATERIALS, AND AS YOU CAN SEE,  YOU  CAN ALMOST



 6       DRAW A LINE ACROSS THAT SAYS THERE  IS  AN EFFECT



 7       OF THE SOLIDS IN THE WATER  ON  THE RECOVERY  OF THE



 8       BASE/NEUTRALS, BUT THERE IS VIRTUALLY  NO EFFECT



 9       ON THE RECOVERY OF THE ACIDS,   V'ELL, THAT'S NOT



10       TERRIBLY SURPRISING; I MEAN, THE ACID  MATERIALS



11       CERTAINLY LIKE THE WATER REASONABLY WELL.   THE




12       SOLIDS CONTENT IN THIS PARTICULAR PLANT WAS 2,6



13       MILLIGRAMS PER LITER, AND THAT'S AWFULLY LOW,  BUT



14       NEVERTHELESS, THERE IS AN OBSERVED  EFFECT,



15            THE SECOND COLUMN, COLUMN  B, IS THE RATIO OF



16       THE RECOVERY SPIKED WITH NO FILTERING  DIVIDED BY THE



I?       RECOVERY SPIKED AFTER FILTERING,  NOW,  THE  SOLIDS ARE



18       STILL THERE IN THE FIRST CASE,  SO THAT WHAT YOU'RE



19       ACTUALLY MEASURING HERE IS HOW WELL DO YOU RECOVER THE



20       PRIORITY POLLUTANTS FROM THE SOLIDS?   YOU'RE NOT TAKING



21       THE SOLIDS AND PRESUMABLY REMOVING  THE PRIORITY



22       POLLUTANTS WITH THEM, BUT REALLY MEASURING  THE



23       EFFECTIVENESS OF YOUR EXTRACTION ON THE SOLID MATERIAL



24       WHILE IT'S STILL PRESENT,   So  THE SMALLER THE VALUE,



25       THE GREATER THE EFFECT OF THE  SOLIDS ON RECOVERY, AND THE
                                  150

-------
1        CLOSER TO IT ONE GETS., THE LESS THE EFFECT, AND IF YOU



2        WANT TO DRAW ANY CONCLUSIONS FROM THAT, YOU CAN,  I



3        DON'T SEE THAT THERE IS A DIFFERENCE,  IT LOOKS TO ME



4        LIKE YOU'RE GETTING EVERYTHING, OR VERY NEARLY EVERY-



5       THING, BACK AS LONG AS THE SOLIDS ARE STILL PRESENT,



6       IN OTHER WORDS, IN THE FIRST CASE, THERE WAS A



7       RECOVERY PROBLEM WHERE THE MATERIAL WAS 'ADSORBED* ON



8       THE SOLIDS, AND THEN WHEN YOU FILTERED THE SOLIDS, YOU



9       TOOK SOME OF THE PRIORITY POLLUTANT WITH THEM,



10            THE SECOND PLANT IS AN INORGANIC CHEMICALS PLANT,



H       MOST OF THE SOLIDS IN THIS PARTICULAR INDUSTRIAL CATE-



12       GORY WERE BORATES BECAUSE OF THE NATURE OF THE PLANTJ 36,3



13       MILLIGRAMS PER LITER FOR THE SUSPENDED SOLIDS, AND AS



14       YOU CAN SEE FROM THE FIRST COLUMN, THERE'S VIRTUALLY



15       NO EFFECT OF THE SOLIDS ON ANY OF THE PRIORITY POLLU-



16       TANTS,  SO WHAT DOES THAT SAY?   IT DOESN'T SAY THAT  IT



17       IS THE SOLIDS THAT CAUSED THE PROBLEM, IT'S WHAT THEY



18       ARE, AND THAT' S BASICALLY THE CONCLUSI ON WE HAVE COME TOj THE



19       SOLIDS CONTENT HERE IS ALMOST AN ORDER OF MAGNITUDE



20       HIGHER THAN IN THE FIRST PLANT WHERE  THERE WAS AN EFFECT;



21       AND  IN THIS CASE, THERE IS NO EFFECT,  So THAT'S NOT



22       TERRIBLY SURPRISING; THE NATURE  OF THE SOLID MATERIAL IN



23       THE  SAMPLE AND THE ADSORPTIVE CHARACTERISTICS OF THAT




24       SOLID MATERIAL AFFECT THE RECOVERY,   AGAIN, VERY LITTLE



25       EFFECT ON THE OTHER SIDE  IN THE  SECOND COLUMN AS WELL,

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 1            THE THIRD COLUMN  IS A  PUBLICLY OWNED TREATMENT
 2       WORKS (POTTO SAMPLE.   IN THIS  CASE, THERE MAY BE
 3       SOME EFFECT OF THE  SOLIDS  IN THE  FIRST COLUMN, AS
 4       YOU CAN SEE,  AGAIN, LITTLE OR NO EFFECT WHEN THE
 5       EXTRACTION  IS CONDUCTED WITH THE  SOLIDS IN PLACE,
 6            THAT'S BASICALLY  WHERE WE ARE, AND LIKE I SAY,
 7       WE ONLY REALLY HAVE DATA HERE  ON  THREE PLANTS,
 8       HE HAVE A FOURTH ONE THAT'S NOW FINISHED;  BY THE
 9       TIME THIS IS DONE,  WE'LL PROBABLY HAVE TEN OR
10       TWELVE, AND AT THAT POINT WE CAN  PROBABLY PRESENT
11       MORE INFORMATION AND BEGIN  TO  GET,  PERHAPS,  A
12       LITTLE MORE STATISTICAL SIGNIFICANCE FROM THE DATA
13       THAT WE'RE GENERATING,  THANK  YOU,
14
15
16
17
18
19
20
21
22
23
24
25
                                  152

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                                                               9
                            QUESTION AND ANSWER
                                  SESSION
 1                              VOICE FROM THE AUDIENCE:  THE
 2       PHENOMENON OF CROSSOVER HAS ALWAYS KIND OF BOTHERED ME.
 3       I  CAN UNDERSTAND THE PHTHALATE SITUATION, SOME ALKALINE,
 4       SAPQNIFICATION OF ESTERS;  ONE  CAN CLASSICALLY EXPLAIN
 5       THAT AWAY.   PHENOL CROSSOVER AT PHIO, PK IS AROUND 9,
 6       9  SOMETHING, 10, YOU CAN EXPLAIN IT THAT WAY, BUT I'VE
 7       ALWAYS HAD SOME PROBLEMS WITH THE PHENOMENON OF APPARENT
 8       CROSSOVER OF SOMETHING LIKE OLEIC ACIDj I'VE DONE
 9       MORE WORK WITH THE ADDITIONAL COMPOUND THAN THE ACTUAL
10       PRIORITY CONSENT DEGREE OF ORGANIC, AND I REALLY WONDER
11       IF THERE IS A SOLUBILITY  PHENOMENON OCCURRING WHERE,
12       SAY,  THE ANION OF A FAIRLY STRONG ACID OR MODERATELY
13       STRONG ACID, LIKE OLEIC,  IS SOLUBLE IN THE ORGANIC
14       PHASE TO SOME EXTENT/OR  IS IT A PHYSICAL PROBLEM  IN
15       THE EXTRACTION ITSELF,   WE ALKALI NIZE THE SOLUTION,
16       TREAT IT WITH ORGANIC SOLVENT, MIX  IT, LET IT SEPARATE,
17       BRING IT DOWN THROUGH THE  SEPARATORY FUNNEL.   I CAN
18       FORESEE THE AN ION 1C HYDROPHOBIC MOLECULE ORIENTING
19       ITSELF AT THE SOLVENT WATER INTERFACE  AND COMING  DOWN
20       AND POSSIBLY BREAKING THROUGH AT THAT  LAST MOMENT
21       WHEN WE'RE TRYING TO GET  ALL OF OUR SOLVENT  OR HAVE  A
22       MATRIX PROBLEM WHERE  IT'S  KIND OF DIFFICULT  TO GET A
23       GOOD SEPARATION, COLLECT  THE ORGANIC MATERIAL, ADD
24       SODIUM SULFATE TO DRY IT,  I CAN SEE A PHYSICAL CARRY-
25       OVER OF THIS SCHIZOPHRENIC MOLECULE  INTO THE DRYING MATERIAL

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        MATERIAL AND THEN BEING  RELEASED,   I  GUESS WHAT I'M
 2      GETTING AT IS, IS THAT POSSIBLE, AND IF SO, IS THERE
        ANYTHING THAT WE CAN DO  TO TEST  THAT  HYPOTHESIS USING,
 o
 4      FOR EXAMPLE, WHAT WE'VE TALKED  ABOUT EARLIER THIS
        MICROEXTRACTION TECHNIQUE WHERE  WE  DON'T SEPARATE THE
        SOLVENT PHYSICALLY, WE JUST TAKE AN ALIQUOT OF THE
 7      SOLVENT AND ANALYZE IT DIRECTLY,  IT JUST DOESN'T MAKE
        SENSE TO ME THAT THESE MOLF.CULES SHOULD GET IN THE
 O
 9      ORGANIC PHASE UNLESS TMFV'RE BEING  PHYSICALLY  CARRIED
10      THROUGH OR THEY'RE CHELATING WITH SOMETHING THAT is
        NEUTRALIZING THE CHARGE  AND MAKING A MORE ORGANIC
         SOLUBLE,  ONE EXAMPLE OF THAT WOULD  BE THE METHYLENE
.,      BLUE CHELATE WITH ORGANIC SULFATES  AND SULFONATES WOULD
I O
14      BE AN ANALOGY THAT I CAN DRAW,
15                             MR- BEIMER:     No,
16                             MR, SPRAGGINS:   BOB SPRAGGINS,
17      RADIAN CORPORATION,  I GUESS MOST OF  us HERE HAVE SEEN
18      EVEN A MORE DRASTIC CROSSOVER  WITH  SOMETHING LIKE
19      NAPHTHALENE WHEN IT'S OCCURRED IN MORE THAN ONE FRACTION
20      AND IT'S HARD TO EXPLAIN WHY IT  WOULD BE,   BOB, ARE
21       YOU GOING TO LOOK AT THESE SOLIDS ELEMENTALLY  TO SEE
22      WHAT'S THERE, WHAT METALS MIGHT  BE  THERE TO CHELATE,
23      FOR INSTANCE; BECAUSE I'LL BET  YOU  IF  YOU LOOK  IN COTTON
24      & HlLKINS, YOU COULD F IND  A METAL  THAT  COULD BE  IN THOSE
25       SOLIDS THAT WOULD CHELATE VERY WELL WITH PHENOXIDE AND

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                                                              .1.
 1       AND ALL ITS SUBSTITUTED DERIVATIVES,  YOU HAD  SAID
 2       THAT PHENOLS LIKE WATER, BUT  I THINK  IT'S ALSO A
 3       PRETTY NUCLEOPHILE, TOO, SO YOU  COULD  PROBABLY  FIND  SOME
 4       INSTANCES WHERE PHENOL WOULD  BE BAD ITSELF.
 5                              MR, BEIMER:   I THINK  DEPENDING
 6       ON THE INDUSTRIAL CATEGORY THAT YOU'RE  LOOKING AT,YOU'VE
 7       GOT A PRETTY GOOD IDEA OF THE TYPE  OF MATERIALS THAT
 8       ARE IN THAT WAS TEWATER,  As  I SAY, THE ONE  THAT  WE WERE
 9       MOST FAMILIAR WITH WAS ONE THAT WE  SAMPLED OURSELVES,
10       AND SO WE KNEW THAT THE SOLID MATERIALS IN THE WATER
11       WERE BORATES, BUT, FOR INSTANCE, WITH THE INORGANIC
12       CHEMICALS PLANT, I HAVE NO HISTORY  ON THAT PLANT,  SO  I
13       REALLY DON'T KNOW WHAT WAS IN THE WATER AND  IT IS NOT
14       PART OF THE STUFF TWAT WE'RE  DOING  TO DETERMINE WHAT  IS
15       THE MAKEUP OF THE SOLIDS,  I'VE GOT A PRETTY GOOD IDEA
16       WHAT THEY WERE  IN THE PQTVI,
17                              MR, TELLIARD:  THE ANSWER  TO YOUR
18       QUESTION IS NO,  HE DOES NOT  DO METALS,  \''.E  DOES  NOT DO
19       WINDOWS NOR DOES HE DO METALS,
20                              MR, SAUTER:  DREW SAUTER,  EPA,
21       I'D JUST LIKE TO OFFER AN OBSERVATION ABOUT  THE CROSS-
22       OVER EFFECT.  YOU KNOW, IT HAS TO HAPPEN,  THE PKA OF
23       PHENOL IS 10 j THAT MEANS THAT HALF  THE  MOLECULES  ARE
24       PROTONATED,  IF YOU TAKE PHENOL AND YOU PUT  IT IT WILL
25       DISSOLVE IN SOLVENT, SO IF IT DOESN'T HAPPEN, THERE*S
                                  155

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 1       SOMETHING WRONG,   As YOU INDICATED,  IT  MAKES SENSE
 2       THAT THE MORE ACIDIC PHENOLS ARE  IONIZED;  THEREFORE
 3       ARE SOLUBLE IN THE ORGANIC PHASE.  ANY  COMPOUND LESS
 4       ACIDIC THAN PHENOL, ALKYOL PHENOLS,  DIMETHYL .PHENOL,
 5       THINGS OF THAT NATURE WILL DO THE  SAME  THING,  So
 6       IT'S REALLY TO BE EXPECTED,  HOPEFULLY,  THE  EXTRACTION
 7       IS DONE IN SUCH A WAY THAT MOST OF IT WOULD  GO TO
 8       THE ACID PHASE, I WOULD THINK, SO THAT NONE OF THAT
 9       STUFF IS SURPRISING,I GUESS,
10                              MR, BEIMER:   I WAS  TRYING  TO
11       POINT OUT, , ,
12                              MR, SAUTER:   JUST ADDRESSING THE
13       CROSSOVER,
14                              MR, BEIMER:   WHAT I WAS TRYING TO
15       POINT OUT IS THE PROCEDURES CALL  FOR PH 11 OR GREATER
16       MEASURED WITH HYDRONIUM PAPER,  THE  DIFFERENCE BETWEEN 11
17       AND 12 is REMARKABLE; IT'S THE DIFFERENCE  BETWEEN
18       KEEPING MOST OF THE ACID SPECIES,  AT  LEAST  ON THE  BASIS
19       OF THESE SURROGATES, KEEPING MOST  OF THE ACID SPECIES IN
20       THE ACID FRACTION AND LOSING UP TO 90 PERCENT OF  THEM
21       IN THE BASE/NEUTRAL FRACTION FOR  THE LESS  ACIDIC  PHENOLS.
22       YOU'RE NOT GOING TO HAVE A PROBLEM WITH PENTACHLOROPHENOL
23       OBVIOUSLY, IT'S ALL GOING TO STAY  IN THE ACID FRACTION,
24       BUT PHENOL ITSELF, YOU RUN THE  RISK OF  RECOVERING 20, 30
26       PERCENT OF IT, DEPENDING UPON THE  PU  AT  WHICH YOU  DO
                                  156

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                                                             13
1       YOUR BASE/NEUTRAL EXTRACTION,
2                              MR, HENDERSON:  JIM  HENDERSON
3       WITH CARBORUNDUM, BOB, LET ME ASK YOU TO  CONFIRM
4       THAT YOU GET MORE CROSSOVER OF ALL  COMPOUNDS WITH
5       LIQUID-LIQUID EXTRACTION THAN YOU DO WITH MANUAL
6      EXTRACTION.
7                             MR, BEIMER:  YES,  THERE'S NO
8      DOUBT ABOUT THAT,  THE EXTRACTION EFFICIENCY  IS
9      SIGNIFICANTLY IMPROVED, WITH THE  EXCEPTION OF THE
10      PAINT PLANT SAMPLES WE'RE RUNNING NOW, WHICH PLUG   THE
11      LIQUID-LIQUID EXTRACTOR,
12                             MR, HENDERSON:   IN SOME CASES
13      THERE ARE  ALSO  CONCENTRATION DEPENDENT  FACTORS,
14      PARTICULARLY WITH POLYNUCLEARS, AS I RECALL, AND  IN
15      SOME CASES COMPOUNDS  LIKE PHTHALATES RUN  VERY WELL
16      AND  IN  SOME CASES YOU GET WILD VARIATIONS.
17                             MR, BEIMER:   I STILL QUESTION
18      WHETHER OR NOT  THE PROBLEM WITH  PHTHALATES  IS ONE  OF
19      CROSSOVER  OR ONE OF CONTAMINATION;  I'M  STILL A LITTLE
20      IFFY ON THAT SUBJECT,
21
22
23
24
25

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158

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1                                  1R,  TELLIARD:   THE  NEXT
2       PART OF THE PROGRAM  IS  GOING  TO  TAKE  A  LOOK AT THE
3       VERIFICATION DATA., OR SOME OF IT,  THAT  WE HAVE BEEN
       GENERATING OVER THE  LAST  COUPLE  OF MONTHS,  NOW,
5      THIS DATA ISN'T AS EXCITING AS THE DATA SUPPLIED
6      BY CHEMICAL MANUFACTURERS GROUP  BECAUSE IT'S  NEW,
7      BUT WE'LL SHOW  IT ANYHOW,   DEAN  NEPTUNE,  WHO  MOST
8      OF YOU KNOW,  IS GOING TO  MAKE THE  PRESENTATION ON
9      THE VERIFICATION DATA,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
                                  159

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             VERIFICATION PROCEDURES -  RESULTS  TO  DATE
                         BY:  DEAN NEPTUNE
 2                                     T
            I  HAVE  A  COUPLE  OF THINGS I  WANT TO SHARE WITH
 3
        YOU  THAT  ARE  NOT EXACTLY ON THIS TOPIC,   MANY OF YOU
 4
        HAVE SEEN IN  THE PAST A MEMO  DEALING WITH THE PRIORITY
 5
        POLLUTANTS  WE HAVE OBSERVED TO  DATE IN THE SCREENING
 6
        ACTIVITIES  ACROSS ALL THE INDUSTRIAL CATEGORIES,  To
 7
        GIVE EVERYBODY AN IDEA OF HOW THINGS ARE CHANGING OR
 8
        NOT  CHANGING,  SINCE  LAST YEAR,  WE HAVE PUT TOGETHER
 9
        AN UPDATE OF  THE PRIORITY POLLUTANT FREQUENCY LISTING,
10
        TABULATIONS,  AND DESCRIPTIONS,
11
            THIS  LISTING INCLUDES MOST  OF THE SCREENING SAMPLES
12
        TAKEN  TO  DATE.
13
            IN CASE YOU ARE  INTERESTED,  I HAVE ABOUT 150 COPIES
14
        AT THE DOOR ON YOUR  WAY OUT,  AND IF YOU'RE NOT INTER-
15
        ESTED, PLEASE LEAVE  IT,  MAYBE SOMEBODY ELSE THAT IS
16
        WOULD  LIKE  TO HAVE THE COPY,
17
            AS YOU  KNOW, THERE HAVE BEEN SEVERAL DIFFERENT
18
        STRATEGIES  THAT WE HAVE DEFINED AT THIS POINT AS
19
        BEING  ACCEPTABLE FOR DEVELOPING VERIFICATION DATA,
20
        ONE  OF THESE  RECENTLY APPEARED  IN THE DECEMBER 3RD
21
        FEDERAL REGISTER, METHODS 62^ AND 625, WHICH is
22
        UTILIZING THE GC/MS  APPROACH,  THE SECOND APPROACH
23
        WAS  THAT  ALSO OUTLINED AND PUT  TOGETHER BY CINCINNATI
24
25       ON METHODS  601 THROUGH 613 WHICH ARE OSTENSIBLY GC

        METHODS WITH  THE EXCEPTIONS BEING ONE HPLC AND ONE GC/HS


   	160	

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       IN THE METHODS 601 THROUGH 613,  IN ADDITION TO EMSL-

1       CINCINNATI GC METHODS .ARE THE ORGANIC CHEMICALS BRANCH

2       WHICH ARE ALSO OSTENSIBLY GC METHODS,
3         AS YOU CAN SEE, WE HAVE A NUMBER OF DIFFERENT
       APPROACHES FROM AN ANALYTICAL STANDPOINT THAT CAN
4       BE USED TO DEVELOP ANALYTICAL DATA,  WHICH ONE IS

5      BEST?  WHICH ONE  IS WORST?  IT DEPENDS,  WHAT IS

6      THE REGULATORY STRATEGY THAT THE PROJECT OFFICER

7      FOR THE INDUSTRIAL CATEGORY IS PLANNING ON USING

8      CAN BE VERY  IMPORTANT  IN WHICH ANALYTICAL STRATEGY

9      IS BEST SUITED,   THE NATURE OF THE SAMPLE MATERIAL

10      CAN DRIVE THE PROJECT  OFFICER  IN ONE DIRECTION OR

11      ANOTHER,  WITH THE ALL GC METHODOLOGIES, THERE IS

12      ALWAYS SELECTED  CONFIRMATION OF A MINIMUM OF 10

13      PERCENT OF THE SAMPLES BY GC/MS,  So IT ISN'T JUST

14      A  NONSPECIFIC DETECTOR THAT WE ARE BASING OUR DATA

15      ON FOR AN  IDENTIFICATION, BUT  IT IS THE CHARACTER-

16      IZATION THAT WILL BE PROVIDED  BY THE GC MEASUREMENT

17      PLUS  A MINIMUM OF 10 PERCENT,  GC/MS CONFIRMATION

18      OF THE  IDENTIFICATION  OF MATERIALS,

19          AS PART  OF THE GC  EFFORT FOR METHODS,601 THROUGH

20      613,  PLUS THE ORGANIC  CHEMICALS BRANCH, THERE ARE A

21      NUMBER OF DIFFERENT ACCEPTABLE COLUMN  PACKING MATERIALS

22      FOR EACH  METHOD,  WE HAVE A SUPPLY  FOR EPA  USE THAT

23      WE HAVE GOTTEN FROM SUPELCO, ALTHOUGH  THERE ARE  A

24      NUMBER OF OTHER  MANUFACTURERS  THAT  EITHER DO OFFER

25      FOR SALE  OR  CAN  OFFER  FOR SALE VERY  SIMILAR PRODUCTS;

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 1       THESE JUST HAPPEN TO BE PROVIDED FOR US UNDER CONTRACT
 2       BY SUPELCO,   ALSO, SUPELCO HAS DONE SOME ADDITIONAL
 3       QUALITY ASSURANCE WORK TO DEMONSTRATE THE UTILITY
 4       OF THE COLUMN PACKING MATERIAL BEFORE WE ACCEPTED
 5       IT,   AT THE DOOR ON YOUR WAY OUT, THERE WILL BE A
 6       LISTING OF ALL THE COLUMN PACKING MATERIALS, BY
 7       METHOD,   THIS WILL BE PARTICULARLY INTERESTING IF
 8       YOU ARE TRYING TO DO SOME GC WORK,   IF IT'S NOT OF
 9       REAL INTEREST TO YOU, PLEASE LEAVE THE COPY FOR
10       SOMEBODY ELSE.
11           WHAT WE WANT TO START TO TALK ABOUT HERE TODAY
12       IS SOME SELECTED RESULTS OF THE VERIFICATION STUDIES
13       TO DATE,   WE'RE GOING TO BE TALKING ABOUT ONE INDUS-
14       TRIAL CATEGORY; THIS IS OUR FIRST LOOK, SO WE DON'T
15       HAVE ANALYSES LIKE THESE TO SHOW YOU ACROSS A LARGE
16       NUMBER OF INDUSTRIAL CATEGORIES,   WE ARE STARTING
17       TO GET ENOUGH DATA SO THAT THIS COULD BE POSSIBLE,
18           AS I  MENTIONED,  THESE RESULTS ARE ON THE VERIFI'
19       CATION STUDIES  TO DATE,   FOR THOSE  OF YOU WHO PERHAPS
20       AREN'T AS FAMILIAR WITH THE TERMINOLOGY AS IT is
21       BEING USED,  LET ME GO BACK AND REFRESH YOUR MEMORY
22       OR GIVE YOU A LITTLE BIT OF INFORMATION THAT WILL
23       HELP YOU WHEN YOU GO BACK AND DO A LITTLE BIT MORE
24       READING,
25
            IN  SCREENING  STUDIES  WE  WERE  TRYING TO MAKE A
                                  162

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1       DETERMINATION OF PRESENCE OR ABSENCE AND AN ESTIMATE
2       OF CONCENTRATION,  BY THE VERY NATURE OF WHAT WE
3      WERE DOING  IN SCREENING, WE WERE ACCEPTING FALSE
4      POSITIVE  IDENTIFICATIONS SO THAT WE DID NOT ELIMI-
5      NATE ANY  COMPOUNDS,  THE REASON FOR THAT IS WE
6      WERE GOING  TO USE THE SCREENING DATA TO FOCUS OUR
7      EFFORTS  IN  VERIFICATION,  WHAT THAT ALL BOILS DOWN
8      TO  is  IF  WE DIDN'T SEE  IT IN SCREENING, THE CHANCES
9      OF  US  MAKING A  CONCERTED EFFORT TO LOOK FOR  IT  IN
10      VERIFICATION WERE VERY  SMALL.  ONLY IF WE HAD SOME
11      OTHER  INFORMATION SUGGESTING THAT WE SHOULD HAVE
12      BEEN SEEING IT  FOR ONE  REASON OR ANOTHER DID WE THEN
13      GO  BACK  AND INCLUDE  PRIORITY POLLUTANT COMPOUNDS
14      THAT WERE NOT OBSERVED  IN SCREENING,  $0 THE SCREEN-
15       ING DATA WAS VERY  IMPORTANT TO US,   IN VERIFICATION,
16      ACTIVITIES WERE FOCUSED BY  SCREENING,  THE OBJECTIVES
17      HERE WERE TO PROVIDE A  CONFIRMATION OF THE  IDENTIFI-
18      CATIONS  OF PRIORITY  POLLUTANTS THAT WERE OBSERVED
19      DURING SCREENING,
20          VIE WERE ALSO TO  DEVELOP  QUANTITATIVE NUMBERS  IN
21      WHICH  WE COULD  STATE SOME CONFIDENCE  FOR THE AMOUNT
22       OF THOSE PRIORITY POLLUTANTS  THAT  WERE  PRESENT,  A
23       THIRD  OBJECTIVE WE  ALSO HAD IN  VERIFICATION  WAS TO
24       USE THIS DATA  TO DETERMINE  THE  OVERALL  TREATMENT
25       CAPABILITIES OF DIFFERENT  POLLUTION  ABATEMENT  SYSTEMS
                                 163

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 1       FOR  REMOVING  PRIORITY POLLUTANT COMPOUNDS,  THESE
 2       WERE THE  STATED  OBJECTIVES TWO YEARS AGOj THEY
 3       HAVEN'T WAVERED  OR  CHANGED ONE BIT,
 4           I  HAVE  A  COUPLE OF THINGS THAT I WANT TO POINT
 5       OUT  TO YOU,   I AM PROVIDING YOU WITH ACTUAL PLANT
 6       SAMPLING  DATA,   NOT CLEAN WATER SPIKES,  NOT A BEST
 7       INDUSTRY, NOT A  WORST INDUSTRY, BUT  ONE  OF THE
 8       INDUSTRIES  IN WHICH WE HAVE DONE QUITE A BIT OF
 9       VERIFICATION  STUDIES TO DATE, AND WHAT WE ARE GOING
10       TO BE  TALKING ABOUT IS POTENTIAL MANIPULATIONS
11       THAT MAY  BE DONE TO MEASURE LABORATORY PERFORMANCE
12       OR A PROJECT  OFFICER FOR A GIVEN INDUSTRIAL CATEGORY
13       MAY  DO TO DEVELOP EFFLUENT DISCHARGE STANDARDS  FOR
14       SPECIFIC  PRIORITY POLLUTANTS,
15           IF YOU  REMEMBER, I STARTED TALKING ABOUT 624
16       AND  625 AND 601  THROUGH 613, AND THE ORGANIC CHEMI-
17       CALS BRANCH METHODS,  THIS DATA IS BASED ON JUST
18       THE  GC/MS METHODS,   THE 624, 625 WITH THE VERIFICA-
19       TION QUALITY  ASSURANCE/QUALITY CONTROL REQUIREMENTS,
20       WHAT WE HAVE  DONE is TO DETERMINE FROM THE DATA
21       COLLECTED THE RECOVERIES FOR EACH OF THE PRIORITY
22       POLLUTANTS  IN THIS  INDUSTRIAL CATEGORY THAT WERE
23       SPIKED,   THE  FORMULA THAT YOU SEE UP HERE IS SIMPLY
24       THAT USED IN  DETERMINING THE PERCENT RECOVERY OF
        THE  SPIKE FROM THIS; IF YOU'LL NOTICE, IT WAS BASED
                                  164

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1       UPON FIVE FACILITIES, FIVE SAMPLING EPISODES, AS
2      WE CALL THEM,  AN EPISODE BEING A VISIT TO ONE
3      PLANT FOR A SAMPLING,
4          THERE WERE FOUR OF THESE PLANTS THAT WERE DONE
5      BY ONE LABORATORY; THE FIFTH PLANT WAS DONE BY A
6      SECOND LABORATORY,  ALL THE DATA IS INCLUDED,  THE
7      OUTLIERS, THOSE DATA THAT WERE DETERMINED TO BE
8      UNACCEPTABLE, WERE DETERMINED BY APPLYING A PLUS
9      OR MINUS TWO STANDARD DEVIATIONS,  SlNCE THIS IS
10      CONSIDERED TO BE A QUANTITATIVE QUESTION AND NOT
11      A QUALITATIVE QUESTION, THOSE DETERMINATIONS IN
12      WHICH THERE WAS 0 PERCENT RECOVERY, I.E., THE SPIKE
13      OF THE PRIORITY POLLUTANT COULD NOT BE RECOVERED,
14      WERE DELETED FROM THE CALCULATIONS AND NOT CONSIDERED,
15      THERE WAS NO QUESTION OR DOUBT WHETHER THE MATERIAL
16      WAS PRESENT OR NOT,  THE SPECTRUM FOR THE MATERIAL,
17      FOR INSTANCE, PHENOL WAS THERE, THE MATERIAL WAS
18      THEREj THEREFORE, IT COULD NOT BE 0 OR ANY NUMBER
19      LESS THAN 0,  So ALL THE VALUES WILL BE SOME NUMBER
20      GREATER  THAN 0 FOR THE RECOVERIES,
21          IN ADDITION TO THAT,  FOR DETERMINING WHETHER THE
22      PARTICULAR RUN WAS ACCEPTABLE OR NOT, AS COMPARED  TO
23      THE INITIAL  LIMITS OF ACCEPTABILITY, DETERMINED ON
24      THE  INITIAL  PHASE, THE LIMITS OF CONTROL WERE
25      DETERMINED ONCE AGAIN BY  USING THE  FORMULA YOU  SEE
                                 JL65.

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 1       UP HERE FOR THE R-C VALUE,  WHERE DOES THIS FORMULA
 2       COME FROM?  IF YOU LOOK IN METHOD 624 AND 625  IN
 3       THE QUALITY ASSURANCE/QUALITY CONTROL DIRECTIONS
 4       THAT WERE INCLUDED IN THE FEDERAL REGISTER DECEMBER
 5       THE 3RD OR IN THE NUMEROUS COPIES THAT WE'VE BEEN
 6       SENDING OUT AND DISTRIBUTING OVER THE PAST SIX
 7       MONTHS, YOU'LL FIND ALL OF THIS INFORMATION IN THE
 8       FORMULA IN THERE, PLUS EXAMPLES OF HOW THEY SHOULD
 9       BE UTILIZED,
10           FOR THIS INDUSTRIAL CATEGORY,  IN THE ACID FRACTION,
11       THE PERCENT RECOVERIES  ARE PLUS OR MINUS TWO STANDARD
12       DEVIATIONS,   THAT WOULD BE CIRCA 95 PERCENT CONFIDENCE
13       THAT ALL OF THE RECOVERY DATA FOR EACH OF THESE
14       COMPOUNDS WOULD FALL WITHIN THAT RANGE.   FOR INSTANCE,
15       PHENOL.  SOME NUMBER GREATER THAN 0, BUT LESS THAN
16       77,3 PERCENT, AS AN EXAMPLE,  THE INDENTED COMPOUNDS
        THAT YOU SEE THERE ARE THE SURROGATE COMPOUNDS,
18         .
            THE NEXT COLUMN PROVIDES THE TOTAL NUMBER OF VALUES
19
        IN THE  CALCULATION, THE NUMBER OF OUTLIERS, IN OTHER
20
        WORDS,  THE NUMBER OF VALUES THAT FOR ONE OF THE REASONS
21       T
        1  GAVE  ABOVE WAS THROWN OUT, AND THE NUMBER OF TIMES
22       n
        Oj IN OTHER WORDS, NO RECOVERY OF THE PRIORITY POLLU-
23                             n
        TANT SPIKE OCCURRED,   ONE OF THE THINGS THAT WE ARE
24
        FINDING IS THAT BETWEEN 30 AND 40 DATA POINTS APPEARS
25
        TO BE AN ADEQUATE NUMBER OF DATA POINTS FROM WHICH TO
                                  166

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1       STARt TO DEVELOP PERCENT RECOVERIES AND POTENTIALLY
2       LABORATORY CONTROL NUMBERS OR DISCHARGE STANDARDS
3       FOR GIVEN PRIORITY POLLUTANT DISCHARGES,  THE REASON
4       WHY I'M POINTING THAT OUT IS THAT, IF YOU WILL REMEM-
5       BER, UNLIKE THE PRIORITY POLLUTANTS, THE SURROGATES,
6      FOR INSTANCE, THE 2-FLUOROPHENOL, THE PENTAFLUROPHENOL,
7       ALPHA/ALPHA-TRIFLUROMETACRESOL AND THE D^ PHENOL,
8      YOU'LL NOTICE THAT THE NUMBER OF VALUES ASSOCIATED
9      WITH THOSE COMPOUNDS IS HIGHER THAN WITH THE OTHERS,
10      THE REASON WHY THEY ARE ALL SPIKED AT 100 PARTS PER
11      BILLION IN EACH SAMPLE,  THEREFORE, THERE IS A LOT
12      MORE DATA BECAUSE EACH AND EVERY SAMPLE WILL LEND
13      US A DATA POINT,
14          YOU'LL NOTICE THERE is QUITE A BIT OF VARIABILITY
15      HERE, BUT ALL THE VALUES THAT ARE OCCURRING  IN HERE
16      ARE PROVIDING US WITH  REASONABLE COVERAGE,   Ip YOU
17      WOULD PLEASE KEEP IN MIND SOME OF THE THINGS YOU'RE
18      SEEING  FOR 2-NITROPHENOL AND 2-CHLOROPHENOL, THE MINIMUM
19      RECOVERY OF  ABOUT 20 PERCENT  IN ONE CASE AND ABOUT 28
20
       PERCENT IN THE  OTHER,
21           IN  THE BASE/NEUTRALS WE ARE SEEING  APPROXIMATELY
22      THE  SAME OVERALL  RECOVERY RANGE.  ONE OF THE THINGS
23      THAT  ALLOWED US TO  POOL MORE  DATA  IS A  T TEST OF THE
24      2X,  THE 10X  AND THE 100X SPIKING  LEVELS AND  THE
25      RECOVERIES ASSOCIATED  WITH  EACH  OF  THOSE SPIKING
                                  167

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 i       LEVELS,  THERE WAS NO DIFFERENCE  IN  THE  PERCENT
 2       RECOVERY BETWEEN ANY OF THOSE LEVELS  FOR ALMOST
 3       EVERY SINGLE PRIORITY POLLUTANT,
 4           WE ONLY HAD ONE OR TWO IN WHICH  THERE WAS A
 5       DIFFERENCE BETWEEN ANY OF THE LEVELS  OF  SPIKING,
 6       AS FAR AS THE PERCENT RECOVERY  IS CONCERNED,  So
 7       ALMOST ACROSS THE BOARD NO DIFFERENCE  IN RECOVERY,
 8       NO MATTER WHAT THE LEVEL OF SPIKING,  NO  STATISTI-
 9       CAL DIFFERENCE,
10           IF YOU WOULD, THE FIRST COMPOUND  UP  THERE, THE
11       1, 2, 'I-TRICHLOROBENZENE WITH THE RECOVERY OF BETWEEN
12       28 AND 92 PERCENT, KEEP THAT IN MIND,  HERE'S A
13       VOLATILE FRACTION AND SOME OF THE THINGS THAT WE'RE
14       FINDING IN THERE.  YOU'LL NOTICE THAT, UNLIKE THE
15       VALUES THAT WE WERE LOOKING AT  IN THE ACID AND
16       THE BASE NEUTRAL FRACTION, THAT A LARGE  NUMBER OF
17       THESE COMPOUNDS ARE PROVIDING US WITH RECOVERIES
18       150 - 200 PERCENT,  OBVIOUSLY,  SOMETHING is OCCURRING
19       WITH OUR INTERNAL STANDARD THAT WE'RE USING FOR
20       QUANTITAT ION,   UNLIKE IN THE ACID AND THE BASE
21       NEUTRAL FRACTION WHERE THE INTERNAL  STANDARD FOR
22       QUANTIFICATION, THE D-JJJ ANTHRACENE,  IS ADDED
23       IMMEDIATELY BEFORE ANALYSIS, IN THE  VOLATILE FRACTION,
24       THE INTERNAL STANDARDS THAT ARE USED  IN  THERE ARE
25       ACTUALLY ADDED TO THE SAMPLE, PURGED  FROM THE SAMPLE,
                                  168

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1       TRAPPED, DESORBED AND THEN SHUNTED  INTO THE  INSTRU-



2      MENT,  OBVIOUSLY SOMETHING is OCCURRING WITH THE



3      INTERNAL STANDARDS AND THEY ARE NOT BEING PURGED,



4      TRAPPED, OR DESORBED WITH EQUAL EFFICIENCIES,



5      THIS MAY VERY WELL LEAD TO SOME SLIGHT ALTERATIONS



6      ON THE PROTOCOL AS TO WHERE THE INTERNAL STANDARDS



7      PERHAPS SHOULD BE ADDED TO PROVIDE  US WITH SOME




8      BETTER DATA,



9           IN THIS PARTICULAR GROUP, THE MAIN THING TO



10      KEEP IN MIND THERE  IS THE 1, 2-TRANS-DICHLOROETHYLENE,



11      THE  FOURTH  FROM THE BOTTOM HERE, AND THE 1,  1, 1~



12      TRICHLORETHANE, WHICH  IS THE THIRD  FROM THE  TOP,



13      THE  REASON  WHY THESE  PARTICULAR COMPOUNDS HAVE



14,     BEEN SELECTED   IS THAT RATHER THAN  TRYING TO PROVIDE



15      A GREAT DEAL OF DATA  ACROSS THE BOARD  FOR EVERYTHING,



16      AND  SELECTED NEITHER  THE BEST NOR THE  WORST  OF ALL



17      THE  VALUES  THAT WE  HAD, TO THEN TAKE ONE MORE  STEP



18      BASED  UPON  THE ACCEPTABILITY OF THE RC VALUES WHICH



19      YOU'LL SEE  FOR  EACH OF THE COMPOUNDS,   THIS  IS BASED



20      UPON PAIRED OR DUPLICATE ANALYSES WHICH  THE  RC WAS



21      CALCULATED,   HOW  A  PROJECT OFFICER  MAY DECIDE  AND



22      SELECT WOULD NOT  BE THE  ARBITRARY  MANNER IN  WHICH I



23      HAVE MADE THAT  SELECTION,  BUT  JUST, AS I  POINTED OUT



24       EARLIER,  JUST  FOR EXAMPLE,  I  COLLECTED A NUMBER  OF



25      DIFFERENT PRIORITY  POLLUTANTS,  NEITHER THE  BEST  NOR



       THE  WORST,  TO  SEE WHAT MINIMUM LEVELS  WE COULD,  WITH



                     	169	

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 1       A STATED CONFIDENCE, MEASURE AND PERHAPS ESTABLISH
 2       LAB CONTROL LIMITS AND EFFLUENT DISCHARGE STANDARDS,
 3       SO IN MAKING THEIR CHOICES THERE WOULD BE A NUMBER
 4       OF POTENTIALLY DIFFERENT REASONS WHY THEY WOULD
 5       SELECT ONE PARTICULAR MATERIAL TO TRY AND REGULATE
 6       VERSUS ANOTHER OR REJECT ONE.
 7           YOU'LL NOTICE THAT FOR ALL OF THEM HERE THE VALUES
 8       ARE CLOSE,   THIS  IS FOR THE 2X OR 20 MICROGRAMS
 9       PER LITER LEVEL AT WHICH THESE VALUES WERE TAKEN,
 10       So WE'VE GOT,  LIKE, FIVE DATA PAIRS PLUS ON THE
 11       CONTINUING PLUS THE INITIAL,   BASED UPON THESE BEING
 12       ACCEPTABLE DATA POINTS WITHIN  CONTROL AS COMPARED  TO
 13       THE INITIAL AND THE CONTINUING VALUES, ONE CAN START,
 14       DEPENDING UPON YOUR STRATEGY,  TO REGULATE A SPECIFIC
 15       PRIORITY POLLUTANT,  FOR THE  2~NITROPHENOL,  A LEVEL
 16       THAT WE CAN MEASURE ON A CONTINUING BASIS ACROSS
 17       THIS INDUSTRIAL CATEGORY WITH  A 95 PERCENT CONFIDENCE
 18
        THAT THE DATA  MEASUREMENT WILL BE CORRECT,  WILL BE 70
        MICROGRAMS PER LITERj  THAT COULD BE AN EFFLUENT
 20       DISCHARGE LIMIT AT THAT LEVEL.   FOR THE 2-CHLOROPHENOL,
 21       100 MICROGRAMS PER LITER,   FOR THE 1,2/hTRICHLOROBENZENE/
 oo
        70 MICROGRAMS  PER LITER,   FOR  THE 1,2-TRANS-DICHLORQ-
 23       ETHYLENE,  30 MICROGRAMS PER LITER, AND FOR THE 1,  L
        1-TRICHLOROETHANE, 30 MICROGRAMS PER LITER.
iyc
            OF COURSE   EVERYONE,  IVl  SURE, REMEMBERS THAT  THE
                                   170

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       DISCHARGE REGULATIONS ARE GOING TO BE BASED UPON

2      TREATMENT TECHNOLOGY RATHER THAN ON SOME ECOLOGICAL

3      IMPACT OR HUMAN HEALTH  IMPACT,  THEREFORE, THE

       NUMBERS THAT WE'RE MOST  INTERESTED IN MEASURING

5      ARE THOSE THAT WOULD BE  ASSOCIATED WITH THE POTENTIAL

6      TREATABILITY FOR THESE COMPOUNDS,  DR, STRYER, USING

7      THE MOLECULAR ENGINEERING APPROACH, AND HE HAS

8      PUBLISHED SEVERAL DIFFERENT VOLUMES ON THIS PARTICULAR

9      APPROACH, HAS PROVIDED  SOME THEORETICAL AND EMPIRICAL

10      CONFIRMATIONS OF VALUES  FOR VARIOUS PRIORITY POLLUTANTS

11      AND THEIR TREATABILITY,  THE  LEVELS THAT HE HAS

12      PROVIDED FOR THE PRIORITY POLLUTANTS ARE WELL WITHIN

13      THE RANGE THAT WE'RE TALKING  ABOUT,  THEY ARE BETWEEN

14      10 AND 100  MICROGRAMS PER LITER.  So WE'RE WORKING

15      IN THE SAME BALLPARK  IN  WHICH HIS MOLECULAR ENGINEER-

16      ING APPROACH SHOWS THAT  TREATMENT OR TREATABILITY

17      HAS A POTENTIAL OF OCCURRING,  DOES ANYBODY HAVE ANY

       QUESTIONS THEY'D LIKE TO ASK?
19

20

21

22

23

24

25
                                   171

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172

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                        QUESTION AND ANSWER

 1                             SESSION


                                  MR,  BEIFIER:   BOB  BEIMER,
 3
        TRW,   I  WOULD  LIKE  TO  OFFER  AN ALTERNATIVE  TO  YOUR
 4
        VOA  RECOVERY WHERE  YOU SAID  THAT  THE  PROBLEM WAS
 5
        PROBABLY BASED ON DIFFICULTIES WITH THE INTERNAL
 6
        STANDARD,   I'D LIKE TO SAY THAT THE WAY THE RECOVERIES
 7
        ARE  MEASURED ON THE VOA PORTION OF THE  ANALYSIS  IS
 8
        THAT YOU DO YOUR SPIKE SAMPLE,  YOU RUN  IT,  YOU TURN
 9
        AROUND AND  SPIKE SUPERCLEAN  WATER AT  A  SIMILAR LEVEL
10
        AND  DO THE  ANALYSIS AND YOU  CALCULATE RECOVERY,   IT
11
        TURNS OUT THAT AT LEAST ONE  OF THOSE  INTERNAL  STANDARDS
12
        IS  IN A  VERY CLEAN  REGION  FOR  MOST OF THE SAMPLES

        THAT WE'VE  EVER DEALT  WITH,  AND I DON'T THINK  THE
14
        PROBLEM  IS  WITH THAT,  BUT  THE  PROBLEM IS WITH  THE
15
        FACT THAT IF YOU SPIKE A REAL  WORLD SAMPLE  YOU CAN
16
        PROBABLY PURGE IT BETTER THAN  YOU CAN DEI ON I ZED OR
17                          T
        SUPERCLEAN  WATER,   THE ALTERNATIVE, OF  COURSE, IS
18
        THAT WHEN YOU  STANDARDIZE  FOR  THE BASE  NEUTRAL OR
19
        ACID FRACTION  SAMPLES, YOU RE  STANDARDIZING WITH
20
        A CONCENTRATION OF  MATERIAL  IN A  SOLVENT AND YOU  RE
21
        INJECTING THAT DIRECTLY INTO THE  CHROMATOGRAPH,
22
        THE  COROLLARY  WOULD BE TO  TAKE YOUR STANDARD AND
23
        EXTRACT  FROM DEIONIZED WATER AND  THEN ANALYZE  IT  AND
24
        CALL THAT YOUR STANDARD, IF  YOU WERE  GOING  TO  RELATE
25
        IT TO THE VOA  PORTION  OF THE ANALYSIS,   WHAT I AM
                                  173

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                                                            ir
 1       SUGGESTING  IS  THAT,  INDEED,  YOU CAN PURGE MANY MATRIX
 2       WATERS  BETTER  THAN YOU CAN PURGE DEIONIZED WATER,
 3       WHEN  YOU  MAKE  UP  YOUR STANDARDS BY PURGING DEIONIZED
 4       WATER,  THAT'S  WHERE  YOUR ERRORS ARE COMING IN OR
 5       YOUR  HIGH NUMBERS FOR RECOVERY.
 6                                 DR,  NEPTUNE:  I THINK YOU
 7       HAVE A CORRECT STATEMENT IN THAT THERE ARE MORE THAN
 8       ONE DIFFERENT  POTENTIAL SUGGESTION AS TO WHAT THE
 9       PROBLEM MAY BE, AND  THERE MAY  BE SEVERAL THINGS
10       INTERACTING,   I WAS  JUST MENTIONING THAT WAS ONE
11       POTENTIAL POSSIBILITY OF WHAT  THE PROBLEM WAS,
12       ONE OF  THE THINGS THAT WAS POINTED OUT THIS MORNING
13       BY  SOUTHWEST RESEARCH INSTITUTE WAS THAT THEY ROUTINELY
14       ADDED SALT TO  THEIR  MICROEXTRACTION TECHNIQUE TO
15       INCREASE  THE YIELD IN THEIR  EXTRACTION,  AND THE
16       DIRTIER THE SAMPLE OR THE HIGHER CONCENTRATION  OF
17       CONTAMINANTS,  ONE WOULD EXPECT A YIELD INCREASE,
18          '                       MR,  BEIflER:   WHAT is  BEING
19       SAID  HERE IS THE  FACT THAT EVEN WHEN YOU USE DEIONIZED
20       WATER TO  PURGE FROM,  YOU HAVE  A MATRIX EFFECT,   WHEREAS
21       IF  YOU  STANDARDIZE SIMPLY BY MAKING UP A KNOWN  CON-
22       CENTRATION  IN  A SOLVENT AND  INJECTING IT INTO A GAS
23       CHROMATOGRAPH  YOU DON'T HAVE ANY OF THOSE MATRIX
24       EFFECTS,  So YOU  WOULD EXPECT  IT IN EVERYTHING ELSE
25       YOU DO  THAT YOU'RE GOING TO  HAVE LESS THAN 100 PERCENT
                                 174

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1       RECOVERY WHEN YOU'RE DOING THE  GC/MS  TYPE  ANALYSIS,
2       THE RIGHT WAY WOULD BE TO MAKE  UP YOUR  STANDARD AND
3      INJECT IT DIRECTLY ON THE COLUMN,, DON'T PURGE IT
4      FROM DEIONIZED WATER, AND YOU'D FIND  ALL YOUR
5      RECOVERIES GO DOWN WELL BELOW 100 PERCENT BECAUSE
6      WE'VE TRIED  IT,
7                                DR, NEPTUNE:   THAT is
8      ONE OF THE OPTIONS THAT WE WERE LOOKING AT,  WHERE
9      DOES ONE ENTER  INTO THE ANALYTICAL  SCHEME, THE
10      STANDARD FOR QUANTIFICATION, AND THAT ONE WOULD
11      BE AT THE SAME  TIME YOU'RE  SWEEPING,  DESORBING FROM
12      YOUR TRAP YOUR  PRIORITY POLLUTANTS, AND SWEEPING
13      IT ON TO THE COLUMN WHICH  IS WHAT YOU'RE SUGGESTING,
14      RIGHT?
15                                 MR, BEIMER:  YES,
is                                 MR, MILLER:  I'M HIKE MILLER
17      FROM  MOBIL  RESEARCH AND DEVELOPMENT AND I HAVE TWO
18      QUESTIONS  FOR  YOU,  THE  FIRST  RELATES TO THE SAME
19      PROBLEM, THE VOAs.  WHAT  INTERNAL STANDARD WERE YOU
20      USING FOR  THATj THE  FEDERAL KEGISTER DOES NOT  SPECIFY
21      A COMPOUND  TO  BE USED AS  AN INTERNAL STANDARD  IN
22      METHOD  624,
                                  DR.,   NEPTUNE: THERE WAS A TOTAL OF
       THREE: CHLOROBROMOBUTANE; THE PROPANE WHICH is SUGGESTED IN THERE,
2b      BUT HAS NOT BEEN AVAILABLE, AND 1,4-DICHLOROBUTANE.
                                   175

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 i                                 MR, FULLER:  THOSE ARE
 2       SUGGESTED  AS  SURROGATE STANDARDS RATHER THAN INTERNAL
 3       STANDARDS.
 4                                 DR, NEPTUNE:  No, THOSE
 5       WERE  THE  INTERNAL STANDARDS,
 6                                 FIR, MILLER:  You USED THEM
 7       AS  INTERNAL STANDARDS; I SEE.
 8                                 DR, NEPTUNE:  YES, FOR
 9       QUANTIFICATION,
10                                 FIR, MILLER:  THE SECOND
11       QUESTION  IS,  ON  MOST OF THE DATA THAT YOU SHOWED
12       UP  THERE,  YOU REJECTED A CERTAIN NUMBER OF OUTLYING
13       DATA  POINTS,   V/HAT WAS THE CRITERIA FOR THEIR REJEC-
H       TION?
15                                 DR, NEPTUNE:  THAT WAS WHAT
16       I WAS TRYING  TO  DISCUSS TO START WITH,  REJECTED DATA
17       WERE  EITHER ZERO VALUES, IN OTHER WORDS, 0 PERCENT
18       RECOVERY,   THE RATIONALE THAT I GAVE YOU FOR NOT
19       ACCEPTING  OS  WAS THAT THIS WAS A QUANTITATIVE PROBLEM
20       AND NOT A  QUALITATIVE PROBLEM,  IT WAS NOT A QUESTION
21       OF  WHETHER THE MATERIAL WAS PRESENT OR ABSENT,
22                                 MR, MILLER:  You HAD TWO
23       COLUMNS UP THERE, ONE WAS THE Osj HOW ABOUT THE OUT"
24       LYING ONES?
25                                 DR, NEPTUNE:  IN THE SECOND
                                   .76

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1       ONE WAS THE OUTLIERS; AS  I MENTIONED, ANYTHING THAT DID
2      NOT FALL WITHIN THE LIMITS OF ACCEPTABILITY WHICH WAS
3      PLUS OR MINUS TWO STANDARD DEVIATIONS,
4                                MR, MILLER:  WAS THE
5      STANDARD DEVIATION SIGMA  DETERMINED WITH  THOSE DATA
6      POINTS  INCLUDED OR WITHOUT THEM?
7                                BR, NEPTUNE:  WITH  THEM,
s                                MR, MILLER:   IN THE FIRST
9      SLIDE THAT  YOU HAD UP THERE, THERE WAS A  SET  OF  DATA,
10       I  THINK IT  WAS THE SECOND LINE  DOWN,  I DON'T  REMEMBER
11      THE COMPOUND  OFFHAND, WHERE  YOU HAD  37 DATA  POINTS
12       INCLUDED,  11  DATA POINTS  EXCLUDED AS  OUTLIERS,
13                                DR,  NEPTUNE:   CORRECT,
i4                                MR,  MILLER:   THAT  MEANS
15       THAT  OUT OF 48 DATA  POINTS,  YOU EXCLUDED 11  OF THEM
16       ON THE  BASIS  OF  THE  FACT THEY  FELL OUTSIDE  TWO SIGMA;
17       THAT'S  NEARLY ONE-QUARTER OF YOUR DATA POINTS, WHEREAS
18       TWO SIGMA SHOULD HAVE ONLY  FIVE PERCENT FALLING
19       OUTSIDE THAT,  HOW IS THAT  MATHEMATICALLY EVEN
20       POSSIBLE?
21                                 DR,  NEPTUNE:    I CAN EXPLAIN
22       THAT FOR YOU,  INITIALLY, IT WAS DETERMINED USING
23       ALL THE DATA POINTS,   IN OTHER WORDS, IN THIS CASE
24       IT WOULD HAVE BEEN SOME 43 DATA POINTS,  AND THE
25       DETERMINATION WAS MADE HOW MANY DATA POINTS OF
                                 122.

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 1      THOSE  FELL OUTSIDE,  AND THOSE OUTLIERS WERE DELETED,
 2      AT THAT  POINT, WHEN  THE INITIAL DATA POINTS WERE
 3      DELETED,  THE  STANDARD  DEVIATION WAS THEN BASED UPON
 4      THE DATA  BASE WITH THOSE OUTLIERS DELETED,   THE QUES-
 5      TION YOU  ASKED ME AT FIRST  WAS WERE THEY INCLUDED IN
 6      THE INITIAL DETERMINATION OF STANDARD DEVIATION,   THE
 7      ANSWER IS YES,  WERE THEY IN THE FINAL?  THE ANSWER IS
 8      NO,
 9                                MR,  MILLER:  So DO I UNDER-
10      STAND  YOU CORRECTLY, THEN,  THAT YOU INCLUDED ALL THE
11      DATA POINTS INITIALLY?
12                                DR,  NEPTUNE:   CORRECT,
13                                MR,  MILLER:  THEN YOU CAL-
14      CULATED TWO SIGMAj THREW OUT THOSE THAT WERE OUTSIDE
15      THAT LIMIT,
16                                DR,  NEPTUNE:   CORRECT,
17                                MR.  MILLER:  RECALCULATED
18      A STANDARD DEVIATION,
19                                DR,  NEPTUNE:   CORRECT,
20                                MR,  MILLER:  DID  YOU AGAIN
21      THROW  OUT THOSE WHICH  WERE  NOW OUTSIDE THE  RECALCU"
22      LATED  TWO SIGMA?
23                                DR,  NEPTUNE:   IF  THERE
       WERE ANY  THAT FELL INTO THAT CATEGORY,  YES,
25                                MR.  MILLER:  So YOU HAD A
                                  178

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1       SMALLER VALUE AND YOU  RECALCULATED  THE  STANDARD
2       DEVIATION, AGAIN THROWING  OUT  ANYTHING  THAT  WAS  OVER
3       TWO SIGMA,
4                                  DR,  NEPTUNE:   CORRECT,
5                                 MR,  MILLER:   NHEN  YOU
6      FINISH, THEN, YOU SAY  THAT 95  PERCENT OF ALL RESULTS
7      SHOULD  FALL  WITHIN  THAT FINAL  CATEGORY?
s                                 DR,  NEPTUNE:   OF THAT  DATA
9      BASE, THAT SELECTED DATA BASE,
10                                 MR,  MILLER:   Is THAT
11      STATISTICALLY SOUND?
12                                 DR,  NEPTUNE:   THE  SELECTION
13      OF DETERMINING  OUTLIERS, WE'VE ASKED THAT SAME QUES-
14      TION  AND  THE ANSWER THAT WE HAVE BEEN  GIVEN  IS YES,
15           SOME  OF  THE THINGS THAT WERE ACTUALLY OCCURRING
16      WITHIN  THE SAMPLES  THAT WERE GIVING SOME OF  THESE
17       RATHER  LARGE RECOVERIES, IN SOME SAMPLE MATRICES,
18      THE Dj_g ANTHRACENE  WHICH WAS USED AS THE INTERNAL
19       STANDARD WAS FOR ONE REASON OR ANOTHER BEING OXIDIZED.
20       ONE OF THE THINGS WE KNOW IT WAS BEING OXIDIZED TO
21       WAS THE ANTHROQUINONE, AND HENCE YOUR  INTERNAL
22       STANDARD, AS IT WAS ADDED, WAS DISAPPEARING, AND
23       AS IT WOULD DISAPPEAR, SOMETIMES AS MUCH AS TWO-THIRDS
24       OF IT WOULD DISAPPEAR WITHIN  A VERY FEW  SECONDS,
25       CONSEQUENTLY ONE WOULD GET A  MUCH  LARGER NUMBER OR
                                  179

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 1      PERCENT RECOVERY BASED  UPON  THE  INTERNAL STANDARD
 2      THERE.  THAT SITUATION  WAS OCCURRING IN THOSE SELECTED
 3      SAMPLES,  ARE THERE OTHER QUESTIONS?
 4                                MR.  ROM:   RESTATE  THE
 5      QUESTION,
 6                                DR,  NEPTUNE:  WHY DON'T I
 7      JUST LET THE GENTLEMAN  WHO RAISED  THE  QUESTION RESTATE
 8      IT,
 9                                MR,  MILLER:   I WAS QUES-
10      TIONING THE STATISTICAL VALIDITY OF  CALCULATING A
11      STANDARD DEVIATION BASED ON  A  SET  OF DATA AND THEN
12      THROWING OUT THE DATA POINTS WHICH FELL OUTSIDE TWO
13      SIGMA. CONTRACTING THAT STANDARD DEVIATION, AGAIN
14      THROWING OUT DATA THAT  WERE  MORE THAN  TWO STANDARD
15      DEVIATIONS OF THE CONTRACTED VERSION,  GETTING A YET
16      SMALLER CONTRACTED VERSION AND AGAIN THROWING OUT
17      DATA, AND FINALLY ARRIVING AT  SOME VALUE WHERE YOU
       NO  LONGER HAD ANYTHING  FALLING OUTSIDE OF PLUS OR
19      MINUS TWO SIGMA AND THEN STATING THAT  IN A TYPICAL
20      SET OF ANALYSES, 95 PERCENT  OF THE RESULTS SHOULD
21      FALL WITHIN THAT VERY NARROW STANDARD  DEVIATION, OR
       PLUS OR MINUS TWO SIGMA,  MY ORIGINAL  QUESTION WAS
23      QUESTIONING THE STATISTICAL  VALIDITY OF REPEATEDLY
       THROWING OUT DATA AND RECALCULATING  THE STANDARD
       DEVIATIONS,
                                 180

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i                                 DR, NEPTUNE:  SEVERAL
2       EXPLANATIONS WERE GIVEN FOR THE NUMBERS THAT WERE
3       BEING DELETED,  THE OBSERVATIONS THAT WERE BEING
4       DELETED WERE THOSE THAT ONE HAD AN EXCUSE FOR OTHER
5       REASONS TO ALSO DELETE.   I GAVE YOU ONE EXAMPLE,
6       THE D-J^Q ANTHRACENE DISAPPEARING,
7                                 MR, MILLER:   IF THAT is
8      THE REASON THAT OUTLIERS  ARE  EXCLUDED, THEN ANY
9      DATA FOR WHICH YOU HAVE REASON TO BELIEVE THEY ARE
10      NOT VALID SHOULD BE EXCLUDED  BEFORE ANY STANDARD
11      DEVIATION IS CALCULATED,  ALL DATA SHOULD BE EXCLUDED,
12                                DR, NEPTUNE:   IT ESSEN-
IS      TIALLY  RESULTED  IN THAT VERY  SAME ACTIVITY OCCURRING,
14                       ,         MS, HOLTZCLAW:  WE DID THIS
15      RATHER  THAN JUST ARBITRARILY  SAYING WE  KNOW THERE
16      WAS A PROBLEM,  ONE OF THE PROBLEMS THAT WE DEAL WITH
i7      is WE DON'T SEE ALL DATA  IN THE  LABORATORY,  WITH THE
18      TWO SIGMA DEVIATION WE WERE ABLE TO DELETE,  IN MANY
19      CASES,  SEVERAL ANOMALOUS  DATA POINTS,   l\(E WENT BACK
20      IN SOME CASES SEVERAL TIMES THROUGH THE DATA NARROW-
21      ING OUR LIMITS,
22          THE REASON WE'RE  DOING THIS  is  NOT  NECESSARILY
23      TO BE SETTING LIMITS  DIRECTLY ON THIS  POINT, BUT  TO
24      GIVE US A CUT TO BE ABLE  TO  GO BACK TO  THE  LABORA-
25      TORIES  AND  SAY,  THESE ARE THE NUMBERS  THAT  WE  FEEL
                                   JLfil

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 1       ARE  FALLING  OUT  OF  RANGE,  LOOK AT YOUR DATA, RECALCU-

 2       LATE YOUR  DATA,  RECHECK YOUR INITIAL REPORTING,  IF

 3       NECESSARY, GO  BACK  AND  RESHOOT THAT SAMPLE; THAT'S

 4       WHAT THIS  FIRST  CUT IS  GIVING US,   IT'S GIVING US A

 5       STARTING POINT TO TRY TO HANDLE THE MASSES OF DATA

 6       THAT ARE COMING  IN,

 7                                 DR,  NEPTUNE:   As I MENTIONED

 8       TO YOU, PERHAPS  THE MOST IMPORTANT PART,  THE OBSERVA-

 9       TIONS THAT ARE DISAPPEARING  ARE ALSO THE  ONES IN
                                                      *
10       WHICH THE  LABORATORY THEMSELVES RAISED A  QUESTION AS

11       TO THEIR VALIDITY,

12                                 MS,  HOLTZCLAW:   IN THE

13       MAJORITY OF  CASES,  THERE IS  A LEGITIMATE  REASON FOR

14       THROWING THEM  OUT,   IN  THE LONG RUN,  WE ARE WORKING

15       WITH STATISTICIANS,  WE  ARE TRYING  TO FIND THE BEST

16       WAY,  BUT WHEN  YOU PICK  ANY STATISTICAL METHOD OF

        WORKING THE  DATA, YOU'RE NOT GOING TO HAVE EVERY-

        BODY HAPPY WITH  IT,  WE MAY  ULTIMATELY HAVE TO SAY
19                                                 .
        WE HAVE TO INCLUDE  THAT NUMBER, BECAUSE IT S JUST
20                            .
        A MATRIX PROBLEM THAT S GOING TO OCCUR,

21                                 MR.  MILLER:  HAVE YOU TRIED
22
        TAKING ACTUALLY  RANDOMLY GENERATED DATA,  GENERATED
23
        ANY  WAY THAT YOU WANT TO,  AND APPLYING THAT SAME
24
        PROCEDURE  TO IT  AND SEEING HOW MANY DATA  YOU CAN
25
        THROW OUT  THAT WAY?
                                   182

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 1   -                              MS, HOLTZCLAW:  No, WE
 2       HAVE  NOT,
 3                                 MR, MILLER:  I SUSPECT
 4       YOU'LL THROW OUT OVER HALF,
 5                                 MS, HOLTZCLAW:  LET ME
 6       GIVE  YOU AN EXAMPLE OF GOING THROUGH THIS,   WE HAD
 7       ONE SET IN WHICH WE HAD ABOUT 30 NUMBERS,   OUT OF
 8       THESE 30,  THE MAJORITY OF THEM FELL WITHIN  THE RANGE
 9       OF 40 TO 70 PERCENT RECOVERY/ AND WHEN I SAY THE
 10       MAJORITY,  I MEAN ABOUT 20 OF THEM,  THE OTHERS,
 11       WE HAD ABOUT FOUR THAT WE COULD LINK DIRECTLY FROM
 12       INFORMATION WE HAD GOTTEN AT THE LABORATORY, THAT HIT
 13       ABOUT 250 OR 500; THE REST OF THEM VARIED UP AND
 14       DOWN,  THERE WERE SOME NEGATIVE RECOVERIES,  THERE
 15       WERE  SOME 0 PERCENT RECOVERIES, THEY VARIED  ON UP TO
 16       ONE THAT WAS AT 1,200,  WE COULD HAVE SET OUR RANGE
 17       TO FIT THAT 1,200, BUT WHEN YOU LOOK AT THE  DATA,
 18       THERE IS SOMETHING WRONG WITH THAT 1,200,   IT GIVES
 19       US A  MANAGEABILITY WITH THE DATA; THAT'S HOW WE'RE
 20       USING IT,
 21                                 MR, MYERS:  I MIGHT SAY
 22       THAT  THAT'S EXACTLY HOW YOU IDENTIFY OUTLIERS IN
 23       ASTK27-77 PROCEDURE.
 24                                 MS, HOLTZCLAW:  IF YOU
25       HAVE  A BETTER SUGGESTION, WE'RE OPEN,  WE'VE BEEN
                                183

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 1       WORKING  WITH  ALL  OF  THE  STATISTICIANS WE CAN GET
 2       TOGETHER AND  NOT  A ONE CAN  GIVE US WHAT EVERYBODY
 3       AGREES  IS A GOOD  WAY OF  THROWING OUT OUTLIERS,
 4                                 MR.  PATTERSON:  A, R,
 5       PATTERSON, ALLIED .CHEMICAL.   THE IDEA OF THE EXER-
 6       CISE  WAS TO EVALUATE THE METHOD AND FIND OUT WHAT
 7       THE RECOVERY  IS,  AND REALLY  WHAT YOU FOUND OUT  IS
 8       THAT  IN  ABOUT TWO-THIRDS OF  THE SAMPLE, YOU'RE  WITHIN
 9       95 PERCENT CONFIDENCE; IN ONE-THIRD OF THE SAMPLES,
10       YOU'RE ALL OVER THE  BALLPARK,
11                                 MS,  HOLTZCLAW:  BUT WE
12       DON'T KNOW WHY YET,
13                                 MR,  PATTERSON:  I KNOW,
14       BUT IT'S STILL THE SAME  PEOPLE USING THE SAME METHOD,
15                                 MS.  HOLTZCLAW:  THAT'S.
16       AGREED,  BUT YOU'VE GOT TO REALIZE THAT WE'RE WORKING
17       IN SEVEN DIFFERENT LABORATORIES,   WE'RE WORKING, IN
18       MANY  CASES, ROUND-THE-CLOCK  SHIFTS; WE'RE WORKING
19       WITH  VARYING  LEVELS  OF TECHNICIANS DOING THE WORK,
20                                 MR,  PATTERSON:  WELL,  THAT'S
21       NOT GOING TO  BE ANY  DIFFERENT FROM THE WAY IT WILL BE
22       USED,
23                                 MS,  HOLTZCLAW:  BUT I'M
24       SAYING WE HAVE TO HAVE SOME  WAY TO GO BACK AND
25       DOUBLE-CHECK  SOME OF THOSE NUMBERS,
                                  184

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                                                           Of-.
                                                           L. *.
1                                 DR, NEPTUNE:  ONE OF THE
2      THINGS THAT MAKES IT LOOK LIKE WE'RE JUST THROWING
3      OUT A NUMBER HERE OUT OF A SERIES AND A NUMBER THERE,
4      THAT is NOT THE CASE.  THESE ARE USUALLY WHOLE SAMPLING
5      EPISODES THAT ARE DISAPPEARING,  IN OTHER WORDS, A
6      WHOLE DAY'S WORTH OF DATA, NOT ONE DATA POINT OUT
7      OF A RUN FOR THAT DAY ARE WE THROWING OUT,
8                                MR. PATTERSON:  DR, ROGERS
9      WAS HERE YESTERDAY, AND  I SHARE HIS OPINION ON THE
10      THING,  IF  I RUN A SERIES OF  MEASUREMENTS AND THEN
11      I CALCULATE 95 PERCENT CONFIDENCE  FOR THOSE MEASURE-
12      MENTS,  I CAN'T,  IF  I THROW OUT A WHOLE BUNCH OF THEM,
13      THEN, OBVIOUSLY, THERE'S ONLY TWO-THIRDS OF THE DATA
14      BEING CONSIDERED AND THAT'S  WHAT MOST OF YOUR MEASURE"
15      MENTS  INDICATED,
16                                DR,  NEPTUNE:   IT MAKES  SENSE
17      FROM  THE STANDPOINT THAT SOMETHING WAS WRONG WITH  THE
18      ANALYSES ON THOSE DAYS AND THIS, ALSO, CONFIRMS THE
19      FACT  THAT  THOSE  SAME  NUMBERS SHOULD  NOT  BE A  PART
20
       OF  THE  DATA BASE,
21                                 MS,  HOLTZCLAW:   WHEN  WE GO
22      BACK,  WE MAY  FIND  THAT ANOTHER THIRD OF  THOSE  FALL
23      BACK IN,   THIS IS  A FIRST CUT OF THE DAY,
24                                 MR,  PATTERSON:   I  MEAN,  THE
25       SAME THING IS LIKELY TO  HAPPEN WHEN SOMEONE  ELSE  DOES
                                  185

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 1      IT LATER ON,
 2                                DR,  NEPTUNE:   THE  SAME  THING
 3      IS LIKELY TO HAPPEN,,,I DON'T  UNDERSTAND THE QUESTION,
 4                                MR,  PATTERSON:   THAT  ONE
 5      SET OF THEM ARE GOING TO BE BAD NUMBERS,,  BUT IT STILL
 6      LOOKS TO ME LIKE TWO-THIRDS CHANCE OF GETTING,,,AS
 7      HIGH AS 95 PERCENT, IF  I RAN THE SAME NUMBERS HERE.
 a                                DR,  NEPTUNE:   OF THE  DATA
 9      BASE, IT'S A 95 PERCENT CHANCE,
10                                MR.  PATTERSON:   NOT ON  THE
11      ENTIRE DATA BASE.
12                                DR,  NEPTUNE:   I  MENTIONED
13      IT WAS A SELECTED DATA BASE AND THERE WAS  A  RATIONALE
14      FOR SELECTING IT,  So ON THE SELECTED DATA BASE,  IT*S
15      TRUE.
16                                MR,  DAVIS:  ABE  DAVIS,
17      HOOKER CHEMICAL,  You REALLY HAVE TWO THINGS YOU'RE
18      CONSIDERING, AND I DON'T THINK IT'S FAIR TO  THROW
19      OUT 0 OR 1,200 PERCENT OR ANY  NUMBER UNTIL YOU
20
       CONSIDER BOTH THE FACT THAT YOU MUST DETERMINE  AN
21      INTERNAL STANDARD WHICH IS ALLOWED TO VARY AND  THE
22      COMPONENT OF INTEREST THAT YOU'RE MEASURING  WHICH IS
23      ALLOWED TO VARY, AND THEREFORE 0 IS JUST  AS  REAL,
24      EVEN THOUGH YOU'VE ADDED MATERIAL TO IT,  AS  110 OR 223
       BECAUSE THAT IS A TRUE NUMBER,  I THINK  THAT, THE LITTLE
                                 186

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        I  KNOW  ABOUT  STATISTICS/  THIS WHOLE PROBLEM IS FRAUGHT

        WITH  NOTHING  BUT PROBLEMS,  TO BE  BLUNT,   YOU'RE TRYING

        TO COME OUT WITH SOME  MEASURE AND I THINK WHAT YOU
 4
        HAVE  TO SAY ON  SOMETHING  THAT YOU THROW OUT THIS

        NUMBER  OF  SAMPLES/  THAT YOU'VE GOT TO GO BACK AND

        CORRECT THE METHOD  AND REALLY NOTHING SHOULD BE

        ACCEPTED,

 8                                 MS, HOLTZCLAW:  HE NEED TO

        GO BACK AND FIRST CORRECT THE NUMBERS IF THEY NEED

10       CORRECTION,   WHAT YOU'RE  SEEING HERE IS A FIRST

11       CUT FROM THAT DATA BASE,   HE HAVE NO WAY OF KNOWING

12       WHEN  WE GET NUMBERS FROM  OUR LABORATORIES IF THEY
13      WERE PROPERLY CALCULATED,
14
15
                                  MR,  MILLER:   As  I  UNDERSTAND
        WHAT YOU'RE SAYING/  THEN/  WHAT YOU'RE SAYING IS THAT
16
        THE DATA BASE ON WHICH YOU DID THESE CALCULATIONS IS

        UNRELIABLE.

18        '                        DR,  NEPTUNE:   No/  INCORRECT,

19                                MS,  HOLTZCLAW:   No/  THAT'S
20               T/
        NOT WHAT I  M SAYING,

21                                MR,  HENDERSON:   WELL/ THE

        THING PEOPLE CAN'T UNDERSTAND AND I  AGREE WITH IT/

23      YOU'RE DETERMINING A PRECISION LEVEL WHICH OUGHT TO

        INCLUDE 19  OUT OF 20 POINTS AND/  IN  FACT, IT ONLY
25
                                187

-------
 1       INCLUDES  12  OUT  OF  20 OR SOME SUCH THING,
 2                                 MS, HOLTZCLAW:  ON A FIRST
 3       CUT.
 4                                 DR, NEPTUNE:  Is THAT A
 5       STATEMENT OR A QUESTION, JlM?
 6                                 MR, HENDERSON:  THAT'S A
 7       SUMMARY OF THE OBJECTION TO THE METHOD OF CALCULATION,
 8                                 MR, TELLIARD:  WAIT,  THE
 9       POOR  PEOPLE  OVER HERE ARE TRYING TO TAKE IT DOWN AND
10       WE  HAVE STRANGE  VOICES APPEARING AND SO FORTH,  IF
11       YOU'RE GOING TO  TALK, GO TO THE MICROPHONE AND IDENTIFY
12       YOURSELF  BECAUSE THEY'RE GOING TO BEAT ME UP IF YOU
13       DON'T DO  THAT,
14                                 MR, HENDERSON:  I'M HOLDING
15       ONTO  THIS MICROPHONE  AND I'M JlM HENDERSON WITH CAR-
16       BORUNDUM,   I THINK  PEOPLE MIGHT BE A LITTLE MORE
        SATISFIED IF, WHEN  YOU CHECK THE NUMBER AND THE
        ANALYSIS  AND THE CALCULATIONS APPEAR TO HAVE BEEN
        DONE  CORRECTLY,  YOU PUT THAT NUMBER BACK INTO THE DATA
20
        BASE,
21                                 DR, NEPTUNE:  RIGHT,
22                                 MS, HOLTZCLAW:  YES,
23                                 DR, NEPTUNE:  IN OTHER
        WORDS, THERE WAS A  REASON FOR EXCLUDING THE NUMBER,
25
        IN  OTHER  WORDS,  IF  THERE WAS A RATIONALE OR REASON
                                 188

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1       FOR EXCLUDING THE NUMBER.  IT WAS THERE.   IN OTHER



2       WORDS.  IN THE LABORATORY,  INDEPENDENTLY OF OURSELVES.



3       WAS PROVIDING THE INFORMATION WHEN THERE  WERE  PROBLEMS



4       WITH NUMBERS OR WITH A  GIVEN RUN,



5                                 MR, MYERS:   THERE  is NO



6      PROBLEM,  YOU CAN GO BACK  AND PUT THAT DATA  POINT



7      BACK  INTO THE DATA BASE AND  RECALCULATE AGAIN,



s                                 MS, HOLTZCLAW:  THAT'S



9      CORRECT,  LET ME  PUT  IT ANOTHER  WAY,   WHAT WE*RE



10      TRYING  JO DO AT THIS  POINT IS TO SET  SOME TYPE OF



11      QUALITY CONTROL LIMITS  ON  THE DATA THAT WE'RE  WORKING



12      WITH. THE REASON  BEING  THAT  WE ARE WORKING WITH DATA



13      FROM  A  NUMBER OF  LABORATORIES;  IN  SOME CASES WE ARE



14      DEALING WITH DATA THAT  IS  GENERATED BY INDUSTRY.



15      AND WE'VE GOT TO  HAVE A COMMON  POINT  AT WHICH  TO



16      START,   A YEAR  FROM  NOW WE'D LIKE  TO  BE ABLE TO TAKE



17      THAT  SUBCATEGORY  AND TELL  PEOPLE THAT WHEN THEY DID



18      SAMPLES IN  THAT  THAT THEY  SHOULD FALL WITHIN THIS



19       RANGE OF PERCENT  RECOVERIES AND  THE  DIFFERENCE



20      BETWEEN DUPLICATE SAMPLES,  WHAT WE  ARE  TRYING TO



21      DO AT THIS  POINT  IS  BEGIN  TO SET SOME QUALITY



22       CONTROL LIMITS  FOR  THAT DATA AND BY  DOING THAT. A



23       QUALITY CONTROL LIMIT OF MINUS  170 PERCENT TO  PLUS



24       350 PERCENT DOES  US  NO  GOOD WHATSOEVER,   So  WE'VE



25       GOT TO TAKE IT DOWN  AND WE'VE GOT TO BEGIN SAYING
                                 189

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1       WHICH NUMBERS ARE OBVIOUSLY PROBLEMS,  NOW, THEY MAY
2      BE MATRIX PROBLEMS,  THEY MAY BE CALCULATION  PROBLEMS,
3      BUT AT THIS POINT THEY ARE PROBLEM NUMBERS,   THEN,
4      WE'VE GOT TO GO BACK AND FIND OUT WHY THOSE NUMBERS
5      ARE PROBLEMS,  1'IE HAD ONE WHOLE EPISODE THAT  DROPPED
6      OUT WHEN WE DID THIS,  THERE MAY WELL BE A PROBLEM
7      WITH THAT PARTICULAR PLANT.  IF THAT'S THE CASE,
8      THOSE NUMBERS NEED TO BE BACK IN THERE,
9          IF, HOWEVER, THE PROGRAM THAT THE PERSON  WAS
10      CALCULATING THEM WITH WAS INCORRECT, THEN THOSE
11      NUMBERS MAY BE NEEDED TO BE THROWN OUT, RECALCULATED,
12      WE ARE NOT SAYING THAT WE'RE GOING TO TAKE A  NUMBER
13      OF 50 PARTS PER BILLION AND MULTIPLY IT BY A  PERCENT
14      RECOVERY OF 50 PERCENT AND COME UP WITH OUR NUMBERj
15      BUT WE ARE SAYING THAT WE'RE TRYING TO BEGIN  TO DO
16      SOMETHING WORKABLE WITH OUR DATA.   VJE'RE TRYING TO
       BEGIN TO GET IT INTO A RANGE THAT WE HAVE SOME CONFI-
       DENCE IN, AND WHAT WE'RE DOING FOR NOW IS THEN GOING
       BACK, LOOKING AT THE DATA,  REWORKING THAT RANGE.
       HOPEFULLY, WHEN WE HAVE ENOUGH DATA, AND WE'RE TALKING
       IN MOST CASES ABOUT 40 TO 50 DATA POINTS, WHICH IS A
       NUMBER OF PLANTS TO HAVE TO ANALYZE IN A SUBCATEGORY,
       THAT WE WILL BE ABLE TO SAY, THIS IS THE CONFIDENCE
24
       THAT WE HAVE IN THIS DATA,   As FAR AS THE POINT ABOUT
25
       DROPPING OS, WE ARE CONSIDERING THOSE TO BE NONDATA
                                190

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1       POINTS AT THIS TIME BECAUSE THEY DON'T TELL US ANY-
2       THING ABOUT THE SAMPLE.  IN OTHER WORDS, WHEN WE
3      HAVE A 0 PERCENT RECOVERY, THEY ARE NOT, AT THIS TIME,
4      TELLING US ANYTHING ABOUT THAT SAMPLE.  NOT WHEN
5      WE'RE TRYING TO ACHIEVE THE CONTROL LIMITS,
e                                DR, NEPTUNE:  HE'VE GOT ONE
7      LAST QUESTION  HERE.
8                                FIR, MYERS:   I DON'T HAVE
9      A QUESTION,  MY NAME  IS HARRY MYERS,  I'M WITH NUS
10      CORPORATION,   IN TREATING ANY BODY OF  DATA, IF YOU
11      ESTABLISH A STANDARD  DEVIATION FOR THAT BODY OF DATA
12      AND APPLY YOUR T VALUES,  IF YOU WANT  TO GO TWO STANDARD
13      DEVIATIONS, YOU WILL  IDENTIFY A CERTAIN NUMBER OF OUT~
14      LIERS,  YOU MUST REITERATE YOUR EVALUATION AND RE~
15      ESTABLISH A NEW STANDARD DEVIATION EXCLUDING THOSE
16      OUTLIERS,
17                                DR, NEPTUNE:  THAT'S EXACTLY
18      WHAT  WAS DONE,
19                                MR, MYERS:   AND  THAT'S
20      EXACTLY WHAT  YOU'RE DOING,   IT EXACTLY FOLLOWS THE
21      PROCEDURES  FOR IDENTIFICATION OF  OUTLIERS  IN ASTM2/-77,
22      THERE'S NO  PROBLEM WITH THAT,
23                                 MR, TAYLOR:  MY  NAME  is PAUL
24      TAYLOR, I'M WITH  CALIFORNIA  ANALYTICAL LABS,   I  HAVE
25      TWO COMMENTS,   FlRST  OF ALL,  DEAN MADE A  MISTAKE IN
                                191

-------
PUTTING THIS SLIDE TOGETHER AND PRESENTING  IT AS, OR
MANY OF US TAKING IT AS. A FINAL PRODUCT,   IT'S
ACTUALLY A WORKING DOCUMENT THAT'S BEING USED TO SET
PERFORMANCE CRITERIA FOR ANALYTICAL LABORATORIES AND
THAT'S EXACTLY WHAT HE'S DOING,  WHETHER THEY THROW
OUT DATA FOR THE FIRST 25 PERCENT OF THE FIRST 40
DATA POINTS IS PERHAPS UPSETTING TO SOME OF YOU, BUT
IF YOU'RE DOING IT YOURSELF IN YOUR OWN LABORATORY,
AND USING IT AS A PERFORMANCE, DEVELOPING A PERFORMANCE
CRITERIA, YOU WOULD PROBABLY DO THE SAME THING AT THE
START,  THE PROBLEM IS, IF DEAN WERE DOING THIS WITH
5,000 DATA POINTS WITH AN ESTABLISHED DATA BASE AND
STILL THROWING THE THINGS OUT, WELL, THAT, YOU KNOW,
ARBITRARILY, AS MANY OF YOU SEEM TO BE TAKING IT,
THEN YOU PROBABLY SHOULD GET A ROPE AND STRING HIM UP,
                          DR,  NEPTUNE:  THANKS, PAUL,
                          MR,  TAYLOR:  I WAS ONLY
TRYING TO HELP, DEAN,
                          DR,  NEPTUNE:  IF YOU WOULD,
PLEASE DON'T FORGET THERE WILL BE TWO HANDOUTS ON
THE WAY OUT, ONE ON THE PRIORITY POLLUTANT FREQUENCY
LISTING AND ONE ON THE GC COLUMN PACKING MATERIAL.
                          MR,  TELLIARD:  ON THE
WAY OUT THERE WILL ALSO BE A SET OF COPIES OF THE
                         192

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1       304H PROPOSED METHODOLOGY,   THERE'S ONLY 120 OF THEM;




2       IF YOU HAVE A COPY,  PLEASE  DON'T TAKE THEM,




3           TOMORROW WE  START  AT 8,   IT'S ONLY 4:30, so IF




4       ANYBODY HAS ANYTHING THEY WANT TO VOICE, VENT, OR




5      WHATEVER, WE'LL  HAVE SOME TIME IN THE MORNING,




6




7




8




9




10




11




12




13




14




15




16




17




18




19




20




21




22




23




24




25
                                 -193.

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194

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                      JANUARY 18, 1980

                        INTRODUCTION
                    BY:  WILLIAM TELLIARD
2

3

4                               W, TFLLIART):  FOR THOSE  OF

5      YOU WHO WERE CORTUNATE ENOUGH TO HAVE AN AGENDA  OF

6      THIS MEETING, A VERY RARE ITEM;I UNDERSTAND,  YESTERDAY

7      WE CUT SHORT AND DID NOT HAVE AN OPPORTUNITY  FOR THE

8      OPEN SESSION, WHICH WAS SOMETHING SCHEDULED DUE  TO THE

9      FACT THAT A NUMBER OF PEOPLE HAD SOME COMMENTS THAT

10      THEY WANTED TO TAKE AN OPPORTUNITY  TO GIVE YOU THEIR

11      THOUGHTS ON A COUDLE OF MATTERS,  Q0 ^OR THE  NEXT  30

12      MINUTES WE WILL BE GLAD TO TALK TO  YOU  ABOUT  ANYTHING

13      YOU WANT,

u                               "1R, R!CF.:   I AM JAMES RICE.

15      I AM A CONSULTING  ENGINEER,   I  AM HERE  TODAY  IN  MY

16      CAPACITY AS A CONSULTANT TO  THE UTILITY lt!ATER Ad  GROUP,

17      WHICH  IS AN AD  HOC ORGANIZATION REPRESENTING  THE STEAM

18      ELECTRIC POWER  GENERATING  INDUSTRY  IN THE  RULE-MAKING

19      THAT EPA IS CONDUCTING,  ONE OF THE ITEMS  THAT WE  ARE

20      VERY MUCH  CONCERNED WITH DEALS  WITH METHOD DETECTION

21      LIMITS,  I GATHER  SOME MENTION  WAS  MADE OF THIS  ON

22      WEDNESDAY;  I WAS NOT ABLE TO BE HERE  FOR THAT MEETING,

23      WE  ARE VERY MUCH CONCERNED  WITH DETECTION  LIMIT

24      DEFINITIONS, PARTICULARLY AS THEY HAVE  APPEARED  IN THE

25      PROPOSED CONSOLIDATED  DRA^T  PERMIT  ON  THE  DEFINITIONS
                                 195

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 1      GIVEN THEREIN  FOR THEM  AND  THE  USE MADE OF THEM,   THAT
 2      PLACES THEM SQUARELY  IN THE EFFLUENT LIMITATION BUSINESS
 3      INASMUCH AS THE APPLICATION BASE  LIMITS ARE A MULTIPLE OF
 4      THE DETECTION  LIMIT FOR METHODS,  SO THAT HOW THAT IS
 5      DEFINED  IS EXTREMELY  IMPORTANT, WE FEEL.
 6            I MIGHT ALSO ADD,  OF COURSE,  THAT OUR INDUSTRY
 7      IS NOT CONCERNED WITH ORGANIC MATTER AS MOST OF YOU ARE,
 8      BUT WE ARE VERY MUCH CONCERNED  WITH THE PRIORITY
 9      POLLUTANT ELEMENTS SINCE THEY APPEAR IN SOME OF OUR
10      DISCHARGES IN  VARYING AMOUNTS,  AND WE ARE CONCERNED
11      THUS  IN  THE CURRENT 30^-H PROPOSALS OF DECEMBER 3RD
12      WITH  THE ICAP  METHODS AND THEIR EQUIVALENCY TO THE
13     . PRESENT  3Q4-H  ASPIRATED AA  AS WELL AS THE 1979 MCAW
14      CONTAINING THE GRAPHITE FURNACE AA METHOD,
15            As  A RESULT OF THAT CONCERN,  AND BOTH OF THESE
16      THINGS RUN TOGETHER, UWAG CONDUCTED IN 1979 AN
17      EXTENSIVE ROUND ROBIN,   THERE WERE INITIALLY SOME
18      31 COOPERATING LABORATORIES,   I DON'T THINK IN ANY
19      CASE  THERE WERE LESS THAN ROUGHLY, AFTER ELIMINATION
20      OF ALL OUTLIERS AND RANKING OF  LABS, AND I MIGHT ADD
21      I AM  REALLY VERY MUCH CONCERNED THAT EPA DID NOT
22      APPARENTLY FOLLOW, AND  I SUGGEST  THEY DO, D-2777,
23      METHOD FOR THE DETERMINATION OF PRECISION AND BIAS OF
24      COMMITTEE D-19 METHODS,  THAT  is  AN EXCEPTIONALLY WELL
25      LAID  OUT PROGRAM FOR  ESTABLISHING PRECISION AND BIAS
                                  196

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1      OF METHODS,   IT GIVES ALL OF THE DETAILS  OF  THE  STATS



2      NECESSARY AND THE  PROCEDURES TO BE  FOLLOWED  TO MAKE



3      DEFINITIVE STATEMENTS ABOUT THE PRECISION AND BIAS



4      OF METHODS, AND I  SUGGEST THAT  IT BE  USED,



5           BUT ANYWAY, THAT ROUND ROBIN SERVED  THE PURPOSE



6      OF GETTING BOTH INTERLABORATORY AND SINGLE LABORATORY



7      PRECISION DATA FOR ARSENIC, CHROMIUM,  COPPER, NICKEL



8      AND ZINC,  WE DID  IT  IN  ONLY TWO MATRICES,   WE WERE NOT



9      IN THE  BUSINESS OF METHODS DEVELOPMENT,   WE  WERE IN THE



10      BUSINESS OF ESTABLISHING AND VALIDATING EXISTING



11      METHODS IN A  WAY THAT WE FEEL,  WE HOPE, WILL BE  A GUIDE



12      FOR EPA IN THEIR VALIDATION OF  METHODS,   So  THAT THE



13      CONDUCT OF THAT WAS IN ONLY TWO MATRICES, THE ^HIO RlVER



14      AT A POINT SOMEWHERE DOWNSTREAM OF  PITTSBURGH, AND ALSO



15      IN THE  EFFLUENT FROM A FLY-ASH  BASIN  ON A LARGE  STEAM



16      GENERATING PLANT,  AND  IT WAS SETTLED  EFFLUENT,   So THAT



17      IN TOTAL THESE WERE IN THE BALLPARK AS BEING THE KINDS



!8      OF MATRICES THAT WE FEEL THAT WE WOULD SEE AND WOULD AT



19      LEAST DEMONSTRATE  THE METHOD  IN SOME  WAY  IN  A RATHER



20      NORMAL  SITUATION,  WE DID THAT,  THAT  INFORMATION HAS



21      BEEN PUBLISHED BY  UWAG,  IT  IS AT THE  PRINTERS, WILL BE



22      DISTRIBUTED AND AVAILABLE TO EPA,   IN FACT,  EMSL



23      CINCINNATI WAS ONE OF THE PARTICIPATING  LABORATORIES  IN



24      THAT PROGRAM,  WE  CONDUCTED  IT  VERY,  VERY STRICTLY  IN



25      ACCORDANCE WITH D-2777,
                                  197

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 1           OUR  CONTRACTOR  WAS P'JUS CORPORATION IN PITTSBURGH,



 2      THEIR  RESPONSIBILITY WAS TO ORGANIZE, RIGHT TO PROTOCOL



 3      THAT WAS  TO  BE  FOLLOWED AND A VERY TIGHT PROTOCOL,   WE



 4      LEFT NOTHING TO INDIVIDUAL CHOICE IN ORDER BECAUSE



 5      WE  FEEL THAT ANY  METHOD IS NO BETTER THAN THE WAY THAT



 6      IT  IS  WRITTEN,  AND THE DATA THAT YOU GATHER IS NO



 7      BETTER THAN  THE WRITTEN METHOD,   YOU MUST ALWAYS KEEP



 8      THAT IN MIND,   IF YOU LEAVE A LOT OF LOOPHOLES, YOU ARE



 9      GOING  TO  GET A  LOT OF SCATTER IN THE DATA,   So THAT



10      WE  TRIED  TO  DO  THIS  THE BEST WE  COULD,  AND I  THINK WE



11      WERE QUITE SUCCESSFUL.   I  MIGHT, FOR YOUR INFORMATION;



12      POINT  OUT THAT SUCH A ROUND ROBIN PROGRAM CONDUCTED



13      ON  THE TWO MATRICES  FOR FIVE ELEMENTS AT BASE LEVEL



14      PLUS FOUR SPIKES  COST APPROXIMATELY $150,000,   IT IS



15      NOT INEXPENSIVE TO CONDUCT ROUND ROBINS', BUT  THE



16      INUDSTRY  FELT THAT THIS WAS ITS  CONTRIBUTION,   WE ARE



17      NOT JUST  HERE TO  CRITICIZE WHAT  OTHERS  ARE DOING, BUT



18      WE  FELT THAT IT WAS  ABSOLUTELY NECESSARY TO PUT OUR



19      MONEY  WHERE  OUR MOUTH WAS, SO WE PUT THIS PROGRAM



20      TOGETHER.



21           BUT  OUT OF THAT, THEN, COMES A NUMBER OF THINGS,



22      FIRST, BY BEING A WELL CONDUCTED PROGRAM WE COULD



23      MAKE VERY ACCURATE STATEMENTS ABOUT OUR RESULTS,  WE



24      COULD  USE THOSE ACCURATE STATEMENTS THEN FURTHER AS



25      A BASIS FOR  DERIVING OR UTILIZING IN DERIVATIONS OF
                                  198

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1       DEFINITIONS FOR LIMIT OF DETECTION AND THE LIKE, SO THAT



2      WE COULD SHOW THE IMPACT OF THESE DEFINITIONS IN A REAL



3      SENSE ON REAL WORLD SAMPLES,



4           ONE OF THE KEY FEATURES OF THIS INTERLABORATORY



5      EFFORT THAT WE PUT ON WAS TO WRITE A PROTOCOL THAT



6      INCLUDED THE SAMPLE BOTTLE AND ITS MANIPULATION IN



7      TRANSMISSION,  WE FEEL THIS IS VITAL IN ANY PROGRAM



8      DEALING WITH SUBSTANCES IN THE MICROGRAM PER LITER



9      LEVEL, THAT THERE IS NO WAY, UNTIL YOU HAVE RUN



10      EXTENSIVELY OVER A LONG PERIOD OF TIME AND A LOT OF



11      MATRICES, OF RULING OUT THE RANDOM ERRORS THAT COME INTO,



12      IN AN INTERLABORATORY SITUATION, THAT PORTION OF THE



13      OVERALL PROCEDURE THAT IS INVOLVED FROM THE POINT AT



14      WHICH A SAMPLE IS SPLIT UNTIL THE DATA IS REPORTED,



15      WE THINK THIS  IS VITAL TO UNDERSTAND THIS DIFFERENCE



16      BETWEEN ANY DEFINITIONS THAT I WILL GIVE YOU THAT WE



17      HAVE DEVELOPED FOR LIMIT OF DETECTION AND SO ON, AND



18      THOSE THAT HAVE BEEN COMMONLY EMPLOYED, AND AS  I



19      UNDERSTAND FROM THE FIRST DRAFT, ARE TO BE PROPOSED BY EP/



20      AS MDUMETHOD DETECTION LIMIT,



21           THE REAL WORLD SITUATION BEGINS IN COMPLIANCE



22      MONITORING WITH WHEN THE TWO PARTIES, THE REGULATED



23      AND THE REGULATOR, GATHER AT AN NPDS DISCHARGE  POINT,



24      COLLECT A SAMPLE, SPLIT IT, AND SEND IT TO THEIR



25      RESPECTIVE LABORATORIES, EACH ONE OF WHICH IS QUALIFIED,
                                   199

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 1      EACH ONE OF WHICH FOLLOWS VALIDATED  AND WELL WRITTEN



 2      PROCEDURES, AND EACH ONE OF WHICH  REPORTS THE RESULTS,



 3      THOSE RESULTS WILL BE DIFFERENT, WE  KNOW THAT,   THE



 4      QUESTION IS, IS THE DIFFERENCE  SIGNIFICANT,



 5      ALSO, THE RESULTS THAT ONE GAINS,  HOW DOES ONE



 6      COMPARE THEM WITH AN EFFLUENT  LIMITATION THAT HAS BEEN



 7      ESTABLISHED, BE  IT AT THE DISCHARGE PIPE OR A WATER



 8      QUALITY STANDARD  IN THE STREAM,   IN  BOTH OF THOSE



 9      SITUATIONS  YOU  ARE DEALING WITH  TWO  PEOPLE,  TWO LABS,



10      YOU CANNOT  JUST LOOK AT WHAT A  SINGLE LAB MIGHT DO



11      BECAUSE ANY ONE LAB, AS YOU WELL KNOW, OPERATING BY



12      ITSELF IN ISOLATION,CAN GET GREAT  REPRODUCIBILITY ON



13      A METHOD,   IT CAN REFINE ITSELF  IN ITS TECHNIQUES AND



14      USE GOOD QC AND IT WILL HAVE A  VERY  PRECISE METHOD,



15      BUT THAT DOES NOT MEAN THAT  ITS  NUMBER CAN BE



16      REPRODUCED  BY SOME OTHER LABORATORY  DOING PRECISELY



17      THE SAME THING WITH JUST AS QUALIFIED PEOPLE AND WITH



18      EXACTLY THE SAME  KIND OF INSTRUMENTATION AND PROCEDURE,



!9           INTERLABORATORY PRECISION  is  A  TERM DEVELOPED



20      TO COVER THAT SITUATION,   IT  IS  ABSOLUTELY THE  ONLY



21      WAY THAT YOU CAN  RECONCILE, OR  AT  LEAST UNDERSTAND



22      AND ASSESS  DIFFERENCES BETWEEN  TWO LABORATORIES, AND



23      THE COMPLIANCE  MONITORING  SITUATION  IS THE DIFFERENCE



24      BETWEEN TWO LABORATORIES AT  THE MINIMUM,  NOW, INTERNALLY;



25      THE SAME DEFINITIONS THAT  I WILL GIVE YOU CAN BE USED
                                   200

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1      SUBSTITUTING ONLY ONE PARAMETER FOR INTERNAL QUALITY
2      CONTROL.  THE BASIS OF OUR DEFINITION, AND REALLY THAT OF
3      EPA% IS NOISE,1 METHOD NOISE,WE LIKE TO SAY, NOT
4      INSTRUMENTAL NOISE. METHOD NOISE, AND THE METHOD IS
5      THE SUM OF THE WHOLE; IT BEGINS WITH THAT SPLIT OF
6      THE SAMPLE, THE SORPTION OR DESORPTION ON THE BOTTLE
7      SURFACE, THE GUY'S THUMBPRINT THAT GOT IN THE CAP THAT
8      YOU DIDN'T KNOW ABOUT, AND ALL THOSE SORTS OF THINGS
 9      THAT OCCUR AS RANDOM COMMON AND UNCOMMON ERRORS THAT
10      CREEP INTO A PROCEDURE.  ONE MUST TAKE THAT INTO
11      ACCOUNT,
12           IN THAT OUTER AREA, THAT INTERLABORATORY PRECISION
13      CAN BE THE BASIS OF A NOISE DEFINITION, AND THAT IS
14      EXACTLY WHAT WE DID,  WE COVERED A SUFFICIENT RANGE
15      OF CONCENTRATIONS IN OUR TEST AND THEN BY DIVIDING
16      OR CURB FITTING IN A WAY, IN OUR CASE IT WAS SERVED BY
17      USING TWO DIFFERENT REGRESSION ANALYSES, ONE OVER THE
1«      WHOLE RANGE OF THE DATA TO EXPRESS THE WHOLE RANGE
19      OF OUR ANSWERS, AND THE OTHER WAS TO EXPRESS OVERALL
20      PRECISION AS A FUNCTION OF THE MEAN CONCENTRATION OF
21      ALL THE PARTICIPATING LABS IN ONLY THE VERY LOWEST
22      END OF THAT RANGE, AND FOR OUR PURPOSES ZERO TO 100
23      MICROGRAMS PER LITER WAS THE LOW END OF THAT RANGE,
24      THEN ONE CAN DETERMINE THE Y INTERCEPT, THE ZERO
25      CONCENTRATION VALUE, AND THE ACCURACY OF ONE'S ESTIMATE
                                  201

-------
 1      OF THAT Y INTERCEPT IS STATISTICALLY ANALYZABLE  ALSO,
 2      SO THAT YOU CAN ARRIVE AT THE VALUE THAT  CONSTITUTES
 3      THE TRUE METHOD NOISE.
 4           IF YOU USE THAT DEFINITION FOR NOISE, YOU CAN
 5      THEN CREATE A WHOLE SERIES OF VERY LOGICAL DEFINITIONS
 6      TO UTILIZE IN COMPARING ANY SET OF RESULTS THAT  YOU
 7      WISH, AS LONG AS EVERYONE UNDERSTANDS THE GROUND RULES,
 8      IN DEVELOPING THESE DEFINITIONS, WE FOLLOWED ALMOST
 9      EXACTLY THOSE THAT WERE PROPOSED IN 1968  IN ANALYTICAL
10      CHEM BY LLOYD CURRIE AT THE NATIONAL BUREAU OF
11      STANDARDS, QUITE A RECOGNIZED EXPERT IN THE STATISTICS
12      OF ANALYTICAL CHEMISTRY,  HlS FIRST LIMIT, AND ONE
13      THAT CORRESPONDS TO THE CURRENT ERA-PROPOSED MDL,
14      REALLY, IN THE FINAL FACT OF IT, SKIP THE TERMINOLOGY;
15      IS CRITICAL LIMIT, AND THAT IS THAT NUMBER THAT  YOU
16      MUST EXCEED TO MAKE THE DECISION AT A GIVEN RISK THAT
17      WHAT YOU GOT, THAT ONE VALUE WAS NOT TRULY ZERO,
18      THAT is LLOYD CURRIE'S CRITICAL LIMIT, THAT HAPPENS TO BE
19      THE ESSENCE OF THE PROPOSED MDL.  Il IS A CONFIDENCE
20      LEVEL, A T-VALUE, SINGLE-SIDED FOR RISK TIMES THE
21      STANDARD DEVIATION OF THE BACKGROUND, OR BASELINE,
22      NOISE AS WE HAVE DEFINED IT, THE Y INTERCEPT OF
23      OVERALL PRECISION VERSUS CONCENTRATION,
24           WHEN YOU START AT THAT POINT, YOU CAN DEVELOP
25      THEN A LOGICAL SERIES OF SITUATIONS, THE  FIRST BEING
                                   202

-------
                                                          9
1       THE  CRITICAL LIMIT WHICH IS THAT POINT AGAIN THAT YOU
2       MAKE THAT DECISION., WAS IT PRESENT, AND YOU HAVE A
3       DEFINITE ASSIGNED RISK,  WE USED A HALF A PERCENT THAT
4       CORRESPONDS TO THE 99 PERCENT CONFIDENCE LEVEL, AND
5       THAT SEEMS TO BE THE ACCEPTABLE ONE IN COMPLIANCE
6      MONITORING,  YOU COULD USE ANOTHER ONE AS LONG AS
7      EVERYBODY AGREES TO WHAT RISK YOU ARE REALLY TALKING
8      ABOUT,   HAVING DONE THAT, YOU CAN THEN CREATE THE
9      NEXT VALUE THAT CuRRIE DOES, AND HE CALLS THAT HIS
10      LIMIT OF DETECTION,  THE LIMIT OF DETECTION IS REALLY
11      THE LOWEST VALUE AT, AGAIN, A STATED CONFIDENCE LEVEL
12      THAT EXCEEDS THE CRITICAL LIMIT,  So THAT IN EFFECT
13      IT IS THE LOWEST VALUE THAT YOU ARE SURE WILL NOT BE
14      REPORTED BY SOMEONE AT THAT 99 PERCENT CONFIDENCE
15      LEVEL AS ZERO,  THAT IS THE NEXT LOGICAL PROGRESSION,
16           NOW THERE IS STILL ANOTHER MEASURE OF THE
17      PERFORMANCE OF A METHOD, AND THAT  IS THE LIMIT OF
18      QUANTIFICATION, OR WE CALLED IT LIMIT OF DETERMINATION,
19      AGAIN FOLLOWING CURRIE.  THE LIMIT OF DETERMINATION
20      INTRODUCES ANOTHER CONCEPT, WHAT SORT OF ERROR ARE
21      YOU WILLING TO TOLERATE NORMALLY IN A RESULT, QUANTIFIED
22      RESULT,  CURRIE, IN HIS DISCUSSION, USES A STANDARD
23      DEVIATION OF 10 PERCENT OF THE AMOUNT PRESENT AS AN
24      ACCEPTABLE ANALYTICAL ERROR, AND THAT  IS FAIRLY COMMON,
25      WE CHOSE IN OUR PROPOSED DEFINITIONS TO USE 29 PERCENT,
                                  203

-------
 1      AND THAT JUST SIMPLY FACES THE  REALITY THAT IN THE



 2      MICROGRAM PER LITER CONCENTRATION  RANGE FOR THE METALS



 3      THAT WE WERE TESTING, THERE ARE SOME  THAT WOULD NOT



 4      QUALIFY AT ALL, ZINC HAPPENED TO ONE  OF THEM,  IF YOU USE



 5      10 PERCENT, BECAUSE THE  STANDARD DEVIATION OF  THE METHOD;



 6      IT NEVER GETS DOWN TO 10 PERCENT,  FOR ZINC IT HAPPENS TO BE



 7      20 PERCENT OR GREATER AT ALL CONCENTRATION LEVELS, SO



 8      WE CHOSE 20 PERCENT,  HAVING DONE  THAT, THEN YOU CAN



 9      ESTABLISH THE LIMIT OF QUANTIFICATION,  OR LIMIT OF



10      DETERMINATION,AS THAT VALUE WHERE  THE LOWEST VALUE



11      WHEREIN THE PRECISION OF THE METHOD  IS EQUAL TO 20



12      PERCENT OF THE LEVEL AT  WHICH YOU  ESTABLISH,



13           So THAT SET OF THREE DEFINITIONS NOW GIVES YOU



14      A REAL GOOD WORKING BASE TO COMPARE WITH ANY OTHER



15      LABORATORYj IF YOU SUBSTITUTE SINGLE LABORATORY



16      PRECISION, WHICH YOU GET IN YOUR OWN  OR THAT WHICH



17      HAS BEEN DEVELOPED AS THE AVERAGE  AS  A POOLED  SINGLE



18      LABORATORY PRECISION AMONG MANY LABS,  THEN YOU ARE



19      ABLE TO FOLLOW THESE SAME DEFINITIONS,  HAVE YOUR OWN



20      CRITICAL LIMIT, UNDERSTANDING THAT IS WITHIN YOUR



21      LAB, IT IS WHAT YOU AS AN ANALYST  CAN SAY STATISTICALLY



22      ABOUT YOUR RESULT, YOU CAN APPLY IT TO YOUR LIMIT OF



23      DETERMINATION AS WELL, BUT ALWAYS  WITHIN YOUR  OWN



24      FACILITY,  IT CAN BE FOR PROCESS CONTROL PURPOSES,



25      IT CAN BE FOR ANY OTHER  THAT YOU NEED,

-------
1            BUT WHEN YOU GO OUTSIDE/ AND YOU ARE IN COMPLIANCE



2      MONITORING, YOU ARE COMPARING TWO LABS, AND WHEN YOU DO



3      THAT YOU MUST USE INTERLABORATORY PRECISION,



4           AS I MENTIONED EARLIER, ONE OF THE KEY FEATURES



5      WAS INCLUSION OF THE PREPARATION OF THE SAMPLE BOTTLE



6      IN THE OVERALL METHOD FOR WHICH INTERLABORATORY PRECISION



7      WAS OBTAINED,  WE CHOSE, AND WE FEEL THIS IS VERY



8      IMPORTANT BECAUSE ABSORPTION, DESORPTION POTENTIAL  IN



9      MICROGRAM PER LITER LEVELS  IN THE CONTAINERS, TO HAVE



10      THE SAMPLE BOTTLES PREPARED BY THE PARTICIPATING



11      LABORATORY,  THEY WERE PURCHASED IN BULK; THEY WERE



12      DISTRIBUTED TO EACH OF THE  PARTICIPANTS; EACH OF THE



13      PARTICIPANTS THEN PREPARED  THAT SAMPLE BOTTLE IN



14      ACCORDANCE WITH THE PROTOCOL; HE WASHED IT, ACID RINSED



15      IT, WASHED IT, DID ALL THE  THINGS THAT WERE NECESSARY;



16      PUT THAT BOTTLE BACK IN A BAG WITH ALL THE ONES THAT



17      HE HAD FINISHED AND SENT THEM BACK TO THE COLLECTION



18      POINT AGAIN, AND OUT IN THE FIELD WHERE THESE BULK



19      SAMPLES WERE OBTAINED AND SPLIT, THEN EACH LABORATORY



'0      HAD HIS SAMPLE BOTTLES FILLED BY OUR CONTRACTOR, NUS,



21      AND RETURNED TO HIM,



22           NOW JUST TO SHOW YOU WHAT THAT DOES, AND WE THINK



23      IS A MAJOR FACTOR  IN THE DIFFERENCE BETWEEN THE SINGLE



24      LABORATORY PRECISION STATEMENTS THAT WE WERE ABLE TO



25      DEVELOP AND THOSE THAT EPA  HAS PUBLISHED  IN THE
                                 205

-------
 i      "1CAW 79, 600/4/79020,   IN  THAT THERE ARE ONLY TWO
 2      PRECISION STATEMENTS,PERIOD/ FOR THE GRAPHITE FURNACE
 3      METHODS AND THEY ARE  FOR ARSENIC AND CHROMIUM,  AT LEAST
 4      AMONG OUR FIVE.  NOW  I  CAN'T SAY THAT THERE MAY NOT BE
 5      SOME FOR OTHER THAT THOSE  FIVE,
 6           FOR ARSENIC AND  CHROMIUM,  ERA'S SINGLE LABORATORY
 7      PRECISION AT THE 50 MICROGRAM PER LITER LEVEL IS
 8      1.1 MICROGRAMS PER LITER FOR ARSENIC AND 0,2 MICROGRAMS
 9      PER LITER FOR CHROMIUM, THAT'S  TOTAL, NOW ALL OF THESE
10      ARE TOTAL ON THE SAMPLE.   UWAG'S POOLED SINGLE
11      LABORATORY PRECISION  FROM  THIS  ROUND ROBIN WAS  5,5
12      MICROGRAMS PER LITER  FOR ARSENIC,  AND 5,1 MICROGRAMS
13      PER LITER FOR CHROMIUM,  A FACTOR OF FIVE FOR ARSENIC
14      AND A FACTOR OF 25 FOR  CHROMIUM, NUMERICAL VALUE FOR
15      PRECISION THAT MUCH LARGER,   WE  ATTRIBUTE THAT  LARGE
16      DIFFERENCE TO THIS EXTENDED PROTOCOL.  I WOULD  URGE,
17      AND WE ARE URGING EPA,  AND I  WOULD URGE ALL OF  YOU
18      IN ANY INDUSTRY, ROUND ROBINS OR  OTHERWISE, TO TAKE
19      THAT FACT INTO ACCOUNT, AND IF  AT ALL POSSIBLE  TO HAVE
20      THE SAMPLE BOTTLE PREPARATION BY THE PARTICIPATING
21      LABORATORY BE MADE PART OF THE  PROTOCOL FOR WHICH
22      YOU DEVELOP THE PRECISION  DATA,
23           THANK YOU,
24                               MR,  TELLIARD:   THANKS,  JIM,
25      ANYONE ELSE WHO WOULD LIKE TO,,,GEORGE.
                                 206

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1                                MR, STANKO:  GEORGE STANKO,
2       SHELL DEVELOPMENT,   WHEN THE BELL RANG ON ROUND 15
3       YESTERDAY AFTERNOON, I  HAD A COUPLE OF QUESTIONS NOT
4       PERTAINING TO STATISTICS,  MAYBE SOMEONE THAT IS HERE
5      COULD ANSWER THESE.
6           I THOUGHT I HEARD SOMEONE SAY, PARTICULARLY DEAN,
7      THAT THE ORGANIC CHEMICAL BRANCH, GC METHODS THAT WERE
8      USED FOR VERIFICATION,  THE PAUL FERINTHALL METHODS,
9      ARE CONSIDERED EQUIVALENT TO THE PROPOSED 601 THROUGH
10      613, DECEMBER 3RD PROPOSAL OF THE FEDERAL REGISTER;
11      AM I CORRECT IN ASSUMING THIS9
12                               MR, TELLIARD:  YES,
13                               MR, STANKO:  THE SECOND PART.
14      DEAN, I LOOKED AT THE HANDOUT THAT WAS GIVEN YESTERDAY
15      WHEN WE LEFT THE ROOM, AND AS FAR AS I COULD TELL, THERE
16      WAS NOTHING IN THAT HANDOUT THAT WOULD INDICATE HOW
17      YOU WENT FROM THE DATA TO THE RC VALUE, AND THEN YOU
18      SORT OF GIVE AN EXAMPLE OF HOW THESE MIGHT BE RELATED
19      TO NUMERICAL VALUE.  Is THERE ANYTHING ON THE PARTICULAR
20      EXAMPLE OR ANYTHING LIKE THAT, COULD IT BE MADE
21      AVAILABLE TO INDUSTRY SO WE CAN FOLLOW YOU?
22                               MR, NEPTUNE:  DEAN NEPTUNE,
23      EPA,  GEORGE, THE DECEMBER ^RD FEDERAL REGISTER HAS
24      EVERY SINGLE FORMULA AND MANIPULATION THAT WAS DONE  IN
25      THERE IN THE EXAMPLED QUALITY ASSURANCE, QUALITY CONTROL.
                                  207

-------
1      I  STATED THAT YESTERDAY WHEN WE  STARTED;  I  WILL REMIND
2      EVERYBODY AGAIN.  EVERY FORMULA  IS  IN  THE DECEMBER  3RD
3      FEDERAL REGISTER NOTICE THAT WAS  PROPOSED FOR  PUBLIC
4      COMMENT,  IT IS ALL PRINTED  IN THEREj  IT  IS ALL THERE
5      FOR YOU, GEORGE.
e                               MR, STANKO:   DEAN, I  FOLLOWED
7      EVERYTHING DOWN TO THE RC VALUE,  BUT HOW  DID YOU GET
8      FROM THE RC VALUE TO THE PROPOSAL OF, SAY, 30 PARTS PER
 9      BILLION FOR DICHLOROBENZENE?
10                               MR, NEPTUNE:   As I ALSO
11      MENTIONED, GEORGE, THOSE WERE THE RC VALUES FOR THE
12      2X LEVEL.  IN OTHER WORDS,  IN THIS  CASE IT  WAS  20
13      MICROGRAMS PER LITER, AS I MENTIONED,   FROM  THAT WE
14      TOOK THE RANGE, THE WORST CASE NUMBER  IN  THE RANGE,
15      WHICH WAS ALWAYS THE LOWEST  RECOVERY,  AND CORRECTED
16      FROM THERE TO WHAT WE SAID WAS A  POTENTIAL  OR  ONE
17      MEANS BY WHICH ONE MAY ESTABLISH  A  VALUE,   IN  OTHER
18      WORDS, WE TOOK THE WORST POSSIBLE CASE, THE MOST
19      CONSERVATIVE, GEORGE, THE ABSOLUTE, AND GAVE IT THE
20      HIGHEST NUMBER THAT WE COULD COME UP WITH,  NOT  THE
21      BEST NUMBER, THE WORST NUMBER, GEORGE.
22                               MR, STANKO:   I WASN'T  TOO
23      CLEAR ON THAT AND I DIDN'T  PICK  THAT OUT  OF THE
24      HANDOUT,
25                               MR, NEPTUNE:   THAT WASN'T  IN
                                  208

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1       ANY OF THE HANDOUTS,  THE TWO HANDOUTS YESTERDAY
2      SIMPLY RELATED TO THE COLUMN PACKING MATERIALS FOR
3      METHODS 601 THROUGH 613, PLUS THE ORGANIC CHEMICALS
4      BRANCH,  THE OTHER HANDOUT SIMPLY RELATED TO, AS I
5      MENTIONED, SCREENING AND THE DATA THAT WE HAD
6      COLLECTED TO DATE ON PRIORITY POLLUTANT FREQUENCY AND
7      VARIOUS DIFFERENT CUTS BY THE INDUSTRIAL CATEGORIES
8      AND CUTS ON THAT VERY SAME DATA,
9                               MR, STANKG:  I THINK THAT
10      CLEARS IT UP,  THANK YOU, DEAN,
11                               f]R, KAGEL:  RON KAGEL, Dow,
12      I WOULD JUST LIKE TO COMMENT ON JlM RlCE'S PRESENTATION;
13      I CERTAINLY SUPPORT HIM,  THERE IS ANOTHER STUDY GOING
14      ON QUITE  INDEPENDENT OF WHAT JlM DID,  IT IS BEING
15      CONDUCTED BY THE ACS, ENVIRONMENTAL COMMITTEE.  THEY
16      HAVE A DRAFT DOCUMENT ON GUIDELINES FOR ENVIRONMENTAL
17      MEASUREMENTS, AND WE HAVE HAD THE OPPORTUNITY TO
18      REVIEW THAT DOCUMENT IN ADDITION TO JlM RlCE'S WORK
19      AND WE SEE THAT THE BOTTOM LINE, THE TWO REACH THE
20      SAME CONCLUSIONS; JIM GETS THERE BY SLIGHTLY DIFFERENT
21      MEANS,  I HAVE MADE THAT AVAILABLE TO SOME OF THE
22      PEOPLE IN THE AGENCY,
23           ON WEDNESDAY WHEN PROFESSOR ROGERS TALKED, ONE OF
24      HIS THREE MAJOR POINTS WAS THAT THE NEED FOR AN
25      INTERMEDIATE, AND HE WAS PUSHING NBS TO KIND OF MEDIATE
                                   209

-------
 1       BETWEEN  THE  INDUSTRIAL HALF AND THE GOVERNMENT HALF WHEN




 2       WE  GET  INTO  THESE REGULATION SITUATIONS,  I THINK




 3       PERHAPS  IN THIS  CASE THE ACS MIGHT SERVE AS A GOOD




        NEUTRAL,  DISINTERESTED THIRD PARTY TO TRY TO WORK OUT




 5       SOME  OF  THE  DIFFERENCES WE HAVE ON THIS, SO I URGE YOU TO




 6       TAKE  ADVANTAGE OF THAT,



 7                                MR,  TELLIARD:  WE ARE NOW




 8       BACK  ON  THE  SCHEDULE AGAIN AND THE NEXT SPEAKER IS



 9       GOING TO  TALK TO YOU A LITTLE BIT ABOUT SURROGATES,



10       IT  IS JlM LONGBOTTOM FROM ENVIRONMENTAL MONITORING AND



11       SUPPORT  LABORATORY IN CINCINNATI,



12



13



14




15



16



17



18




19




20



21



22




23



24



25
                                  210

-------
 i                EVALUATION OF CANDIDATE COMPOUNDS
 2                       AS SURROGATE SPIKES
 3                       BY:  JIM LONGBOTTOM
 4
 5            THE DISCUSSIONS THAT WE HAVE HAD so FAR IN THE
 6       MEETING HAVE CONCENTRATED IN TWO AREAS THAT ARE OF
 7       CONCERN:  PROBLEMS WITH THE METHOD, AND QUALITY
 8       CONTROL PROCEDURES THAT ARE IN USE OR PROPOSED,
 9       THE PROBLEMS OF THE METHODS THAT WE WERE TALKING
10       ABOUT CAN BE DIVIDED INTO REACTIONS BETWEEN THE
11       PRIORITY POLLUTANTS AND REACTANT MATRICES, CARRY-
12       OVER OF THE PHENOLS AND BASE/NEUTRALS INTO OTHER
13       FRACTIONS, AND THE PROBLEM WITH SOLIDS AND THEIR
14       EFFECT ON RECOVERIES,
15            THE QUALITY ASSURANCE PROCEDURES ARE THE ONE
16       THAT DEAN NEPTUNE DISCUSSED IN DEPTH YESTERDAY
17       THAT HAS BEEN OFFERED AS AN EXAMPLE IN THE
18       DECEMBER 3RD FEDERAL REGISTER USING RC VALUES FOR
19       DETERMINING PERFORMANCE CRITERIA, AND THE ISOTOPIC
20       DILUTION APPROACH THAT IS BEING WORKED ON OUT AT
21       SYSTEMS, SCIENCE AND SOFTWARE BY BRUCE COLBY,
22            WE HAVE BEEN LOOKING AT ANOTHER POSSIBLE
23       APPROACH TO TRY TO TAKE ADVANTAGE OF THE EMSL
24       REPOSITORY, WHICH IS CURRENTLY GATHERING UP A
25       COLLECTION OF ALL THE PRIORITY POLLUTANTS FOR
                                 211

-------
 1       DISTRIBUTION TO ANYONE WHO WILL WANT THEM  IN THE
 2       FUTURE,  l!lE ARE LOOKING AT INTERNAL STANDARD
 3       COMPOUNDS, SPIKING SOLUTIONS AND SURROGATE SPIKES
 4       TO OFFER THROUGH OUR REPOSITORY,  So WE HAVE
 5       BEEN TRYING TO EVALUATE THE MOST EFFECTIVE USE
 6       OF SURROGATES,  IT APPEARS FROM A PRACTICAL
 7       STANDPOINT THE SURROGATES, HOWEVER THEY ARE
 8       USED, WHETHER IT IS BY ISOTOPIC DILUTION OR IN
 9       SOME OTHER WAY SUCH AS WHAT IS BEING USED BY
10       DEAN'S PROGRAM, OFFER THE BEST HOPE FOR A CONTROL
11       MONITORING PROCEDURE FOR THE PRIORITY POLLUTANT
12       ANALYSIS AT A REASONABLE COST,
13            WE ARE EVALUATING DATA TO FIGURE OUT THE
14       BEST WAY TO USE SURROGATE SPIKES, AND I WOULD
15       LIKE TO JUST OFFER UP ONE POTENTIAL APPROACH
16       TO IT,  AS I MENTIONED, ONE OF THE THINGS THAT
17       WE HAVE BEEN DISCUSSING IS THE PROBLEMS IN THE
18       METHOD,  IF WE START THERE AND RECOGNIZE THE
19       WEAKNESS OF THE METHODS AND IDENTIFY THE PROBLEM
20       COMPOUNDS ON THE PRIORITY POLLUTANT LIST, WE
21       CAN CONCENTRATE ON THOSE COMPOUNDS AS WE ATTEMPT
22       TO DEVELOP PERFORMANCE CRITERIA,
23            THE SECOND STEP WOULD BE TO USE THE PROBLEM
24       AREAS OF THE METHOD TO SELECT OUR SURROGATE
25       SPIKES,  THIRD, WE COULD ESTABLISH RECOVERY
                                  212

-------
 1       CRITERIA FOR THESE MATERIALS AND USE THE CRITERIA
 2       TO IDENTIFY PROBLEM SAMPLES AND PROBLEM ANALYSES,
 3       THEN,  FOR THAT FRACTION OF THE COMPOUNDS, OR
 4       FRACTION OF THE SAMPLES THAT FAIL TO MEET THE
 5       PERFORMANCE CRITERIA, WE IDENTIFY THAT THERE IS
 6       A PROBLEM,  WHETHER IT IS A MATRIX EFFECT OR
 7       SOLIDS OR WHATEVER,  THEN WE ESTABLISH A PROTOCOL
 8       FOR FOLLOW-UP ACTION, DEVELOPING ADDITIONAL
 9       STEPS  TO DEFINE WHAT IS DONE IF YOU DO NOT GET
10       ACCEPTABLE RECOVERY,   THEN WE CAN CONCENTRATE
11       OUR QA AND QC EFFORTS ON THE PROBLEM SAMPLES,
12       RATHER THAN ARBITRARILY RUNNING EVERY TENTH
13       SAMPLE OR SPIKING 100 PERCENT OF THE SAMPLES WITH
14       ALL OF THE PRIORITY POLLUTANTS, OR ANY OF THE
15       OTHER  APPROACHES THAT HAVE BEEN DISCUSSED HERE,
16            IN SUMMARY,  THE APPROACH I AM SUGGESTING
17       WILL ESTABLISH CRITERIA TO SORT OUT THE GOOD
18       SAMPLES FROM THE BAD SAMPLES AND THEN REQUIRE
19       ADDITIONAL EFFORT TO DEFINE THE APPLICABILITY OF
20       THE METHOD TO THE BAD SAMPLES,
21           THE PRINCIPAL ADVANTAGE OF THIS APPROACH
22       WOULD  BE IF WE HAD PERFORMANCE CRITERIA FOR THESE
23       PARTICULAR SURROGATES,  WE COULD ELIMINATE THE
24       NEED FOR THE FRONT-END DEVELOPMENT OF PC VALUES
25       AND CRITICAL LIMITS AND EVERYTHING ELSE,  WE WOULD
                                 213

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 1       SIMPLY ANALYZE THE SAMPLE, AND  IF WE MET ALL



 2       PERFORMANCE CRITERIA FOR OUR SAMPLE, THEN THAT



 3       IS IT,  IF WE HAVE CHECKED OUR  PROBLEM AREAS,



 4       THEN IT IS NOT A PROBLEM SAMPLE, AND THE RESULTS



 5       WOULD BE ACCEPTABLE,



 6            TO TRY TO EVALUATE SOME OF THESE PROBLEM



 7       AREAS, I HAVE BEEN LOOKING AT THE CARBORUNDUM



 8       ACCURACY AND PRECISION REPORTS THAT ARE BEING



 9       DEVELOPED FOR EFFLUENT GUIDELINES,  IF WE LOOK



10       AT THE PURGEABLES, CARBORUNDUM, LIKE MANY OF



11       THE CONTRACTORS, USES THE BROMOCHLOROMETHANE



12       AND 1,4-01CHLOROBUTANE AS INTERNAL STANDARDS



13       IN THE METHOD AND CALCULATES CONCENTRATIONS FROM



14       THEM,   IN THEIR STUDY THEY LOOKED AT PERHAPS



15       HALF A DOZEN OTHER SURROGATE SPIKES THAT WERE



16       BEING USED IN THE AFFLUENT GUIDELINES DIVISION



17       TO DEFINE, HOPEFULLY, RELATIONSHIPS BETWEEN



18       PRIORITY POLLUTANT RECOVERIES AND SURROGATE



19       SPIKES,



20            IN THE PURGEABLES, I THINK IT IS MOST



21       IMPORTANT THAT IF WE ARE GOING TO USE THE INTERNAL



22       STANDARD PROCEDURE, THAT WE COME UP WITH AN



23       INTERNAL STANDARD THAT IS OUR BEST SURROGATE,



24       IF YOU WANT TO SELECT A SURROGATE IN TERMS OF



25       ITS RECOVERY BEING IDENTICAL TO THE OTHER COMPOUNDS
                                 .214.

-------
 1       BEING  MEASURED, IN THE CASE OF THE VOLATILE



 2       PROCEDURE WE  ARE TALKING ABOUT,  THAT SHOULD BE



 3       OUR  INTERNAL  STANDARD,   THAT IS  THE ONE THAT



 4       SHOULD BE USED TO CALCULATE ALL  OF OUR RESULTS,



 5       NOT  TO MONITOR OUR QUALITY CONTROL.  So IN LOOKING



 6       AT THE VOLATILE DATA, WE CONCENTRATED ON WHICH OF



 7       THE  COMPOUNDS COULD SERVE AS THE BEST INTERNAL



 8       STANDARD OF THE ONES THAT WERE BEING USED,  WE



 9       EVALUATED ^  METHYLENE CHLORIDE, D^ DICHLOROETHANE



10       AND  Djj TRICHLOROETHANE AS INTERNAL STANDARDS,  FOR



11       EXAMPLE,



12            IF WE SWITCHED OUR DATA BASE USING THESE



13       COMPOUNDS, ARBITRARILY CALLING THEM THE INTERNAL



14       STANDARD, AND RECALCULATED OUR DATA BASE,  COULD WE



15       IMPROVE THE DATA BASE?  A.RE THESE DEUTERATED



16       COMPOUNDS BETTER INTERNAL STANDARDS THAN THE ONE



17       ACTUALLY USED?  AFTER STEPPING THROUGH SOME OF THE



18       CALCULATIONS, WE FOUND THAT, NO, THE DATA DID  NOT



19       IMPROVE BY USING ANY OF OUR SURROGATE SPIKES AS



20       THE  INTERNAL  STANDARD,   HE INVESTIGATED A LITTLE



21       DEEPER AND REALIZED THAT WE WERE GETTING ISOTOPIC



22       INTERFERENCES FOR THOSE COMPOUNDS SUCH AS DEUTERATED



23       METHYLENE CHLORIDE,  THE SURROGATE SPIKE RECOVERIES



24       CORRELATED VERY NICELY WITH THE  SPIKED CONCENTRATION



25       LEVELS OF METHYLENE CHLORIDE, FOR EXAMPLE,  BRUCE

-------
 i       COLBY TELLS ME THAT I NEED TO APPLY HIS  ISOTOPIC
 2       DILUTION MATHEMATICS TO RESOLVE THE DATA,
 3            WE GOT TO WONDERING WHAT YOU WOULD  DO WITH
 4       A SURROGATE SPIKE IF YOU WERE LOOKING AT THE
 5       WEAKNESS OF THE METHOD, IN THIS CASE, PURGE AND
 6       TRAP,  IF YOU WANT TO MONITOR, FOR EXAMPLE, TRAP
 7       BREAKTHROUGH, YOU MIGHT COME UP WITH A FREON AND
 8       CHECK FOR BREAKTHROUGH OF THE FREON,  YOU MIGHT ALSO
 9       ADD A COMPOUND THAT DOESN'T PURGE VERY EFFECTIVELY
10       TO MONITOR FOR MATRIX EFFECTS,  HOWEVER, SINCE THE
11       MAJORITY OF THE PURGEABLES ARE HALOGENATED, IT IS
12       VERY DIFFICULT, WITHOUT GETTING INTO ISOTOPIC DILUTION
13       CALCULATIONS, TO COME UP WITH A COMPOUND, A DEUTERATED
14       COMPOUND, AT ANY RATE, WITH ION FRAGMENTS THAT COULD
15       BE CLEANLY RESOLVED FROM THE NONDEUTERATED FORM OF
16       WHAT YOU ARE MEASURING,  So WE HAVE BEEN KIND OF
17       GOING IN CIRCLES,
18            LET'S LOOK AT THE PROBLEM AS (1) WHAT ARE YOU
19       TRYING TO MEASURE; (2) WHAT ARE THE MECHANICAL
20       PROBLEMS OF THE METHODj AND (3) WHAT ARE THE LIKELY
21       MATRIX EFFECTS,  THEN LET'S SET UP OUR CONTROLS
22       FOR A SYSTEM TO SEPARATE GOOD DATA FROM  DATA THAT
23       NEEDED FURTHER DEFINITION OR INVESTIGATION,
24            To MONITOR THE MECHANICAL PROBLEMS, WE MIGHT KEY
25       IN ON THE ACTUAL AREA COUNTS THAT ARE BEING GENERATED
                                 -216.

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                                                           7
1      BY  EACH  OF  OUR  INTERNAL  STANDARDS,   THE ANALYST



2      COULD  PERFORM AN  INTERNAL OR  EXTERNAL STANDARD



3      CALIBRATION WITH  THE  FIRST RUN,  THEN CALCULATE



4      ALL OF HIS  SAMPLES  BASED ON THE  INTERNAL STANDARD,



5      BUT ALSO CHECK  THE  ACTUAL AREAS  GENERATED BY



6       INTERNAL STANDARDS  IN EACH RUN AGAINST WHAT THEY



7      SHOULD BE,  BASED  ON THE  PURE  WATER  MATRIX.   WE



8      COULD  DEVELOP AN  ACTION  BASED ON THE AREAS,  IF



9      YOUR INTERNAL  STANDARD AREA COUNT FALLS BELOW OR



10      ABOVE  A CERTAIN LEVEL, THEN YOU  SHOULD REPEAT THE



11      ANALYSIS,  IT  SEEMS LIKE ONE  OF  THE THINGS THAT



12       HAPPENS IS  THAT INSUFFICIENT  INTERNAL STANDARD IS



13       ADDED, OR TOO  MUCH  INTERNAL STANDARD, AND ALL THE



14       NUMBERS CALCULATE OUT VERY HIGH  OR VERY LOW,  THAT



15       IS AN  EXAMPLE  OF WHAT PRISCILLA  HOLTZCLAW WAS



16       MENTIONING  YESTERDAY; WHEN YOU LOOK AT DATA AND SEE



17       A PATTERN LIKE THAT,  YOU KNOW THERE IS A PROBLEM,



18            IF WE  USE THE  INTERNAL STANDARD APPROACH,



19       ANOTHER PROBLEM THAT KEEPS COMING UP WITH THE  ,



20       PURGEABLES  IS  BACKGROUND CONTAMINATION,  I DON'T



21       FEEL THAT A FIXED PROGRAM TO CALCULATE CONCENTRATIONS



22       FROM ONLY ONE INTERNAL STANDARD  IS ADEQUATE,  As YOU



23       SET UP YOUR CONTROLS, YOU SHOULD USE TWO OR THREE



24       INTERNAL STANDARDS,  YOU CHECK AREAS  IN YOUR MATRIX



25       AGAINST THE RESPONSE  IN YOUR STANDARD, THEN SELECT
                                  212.

-------
THE INTERNAL STANDARD BASED UPON BEST AGREEMENT



WITH YOUR FIRST STANDARD RUN OF THE DAY,



     AS AN EXAMPLE, IN THIS PARTICULAR DATA BASE



THAT WE WERE LOOKING AT, BECAUSE OF CONTAMINATION



FROM THE UNDEUTERATED FORMS OF THE SURROGATE SPIKES,



BROMOCHLOROMETHANE TURNED OUT TO BE THE BEST INTERNAL



STANDARD TO USE FOR THE EARLY ELUTERS,  HOWEVER,



THIS COMPOUND IS FOUND REGULARLY IN DRINKING WATERS



AND RIVERS, SO WE MAY WANT TO GO TO A LABELED FORM



OF THAT COMPOUND TO EVEN FURTHER ENHANCE OUR ABILITY



TO GET USEFUL DATA USING IT AS AN INTERNAL STANDARD,



     IF WE LOOK AT THE ACID FRACTION, WHERE WE ARE



ENCOUNTERING CARRY-OVER OF PHENOLS INTO THE BASE/



NEUTRAL FRACTION, WE COULD AGAIN CONSIDER THE



WEAKNESSES OF THE METHODS,   THE CARBORUNDUM DATA



GENERALLY CORRELATES PKAs WITH CARRY-OVER,  WE



SHOULD CONCENTRATE ON A PERFORMANCE CRITERIA FOR



THE RECOVERY OF A DEUTERATED WEAK ACID, FOR EXAMPLE,



DIMETHYLPHENOL, THE WEAKEST ACID IN THE GROUP,   IN



THAT CASE, WHERE WE DIDN'T ACHIEVE A RECOVERY THAT



MET THE CRITERIA, WE SHOULD ANALYZE THE BASE/NEUTRAL



FRACTION FOR THE PHENOLS AND ADD UP THE TOTAL.   So



IN THOSE CASES WHERE WE DO HAVE CARRY-OVERS AND DO



NOT ACHIEVE AN ACCEPTABLE RECOVERY OF OUR WEAKEST



ACID,  WE WOULD AUTOMATICALLY RUN THE BASE/NEUTRALS
                          218

-------
 1       TO PICK UP THE CARRY-OVER TO ADD UP THE TOTAL,
 2       THESE ARE THE TYPES OF THINGS THAT WE COULD
 3       CONSIDER,
 4            FOR THE STRONGER ACIDS, WE WOULD NEED A
 5       SURROGATE TO MAKE SURE THAT OUR PH WAS LOW ENOUGH,
 6       WE MIGHT WANT TO MONITOR THIS USING A LABELED
 7       NITROPHENOL.  I THINK WE NEED,, AGAIN, TO HAVE MORE
 8       THAN ONE INTERNAL STANDARD WORKED INTO THESE METHODS
 9       BECAUSE OF THE POSSIBILITY OF CHEMICAL REACTION FOR
10       THE INTERNAL STANDARDS AND THE POSSIBILITY OF
11       INTERFERENCES,
12            FOR THE BASE/NEUTRALS, I THINK WE COULD LOOK
13       FOR ADDITIONAL CONTROLS,  WE WOULDN'T HAVE TO
14       DEMONSTRATE THAT OUR INITIAL PK WAS HIGH ENOUGH TO
15       EXTRACT THE BASES, SINCE WE CAN MONITOR PH WITH A
16       WEAK ACID, BUT WE SHOULD BE INTERESTED IN DEVELOPING
17       SURROGATES FOR THOSE COMPOUNDS THAT ARE SENSITIVE
18       TO CHEMICAL REACTION AND THOSE MATERIALS SUCH AS
!9       THE LARGER PAHs THAT ARE DIFFICULT TO EXTRACT IN
20       THE PRESENCE OF SOLIDS TO MONITOR FOR THAT MATRIX
21       EFFECT,
22            WHERE THE SURROGATE RECOVERY IDENTIFIES WHAT
23       IS CLEARLY A MATRIX EFFECT, SUCH AS IN THE CASE OF
24       SOLIDS, LOW RECOVERY FOR OUR PAH INDICATOR, OUR QC
25       PROTOCOL COULD REQUIRE THAT WE HAVE THAT SAMPLE
                                  219_

-------
 1       SPIKED WITH PRIORITY POLLUTANTS AND DEVELOP A
 2       RECOVERY STATEMENT FOR THAT SAMPLE TO DEFINE WHAT
 3       ACTUALLY IS GOING ON IN THAT MATRIX,
 4            THAT is THE APPROACH THAT WE ARE CURRENTLY
 5       EXAMINING,   WE ARE INTERESTED IN MINIMIZING AS MUCH
 6       AS POSSIBLE THE OVERHEAD COST OF RUNNING 15 SAMPLES
 7       UP FRONT TO DEFINE THE OPERATOR'S INDIVIDUAL
 8       PERFORMANCE LIMIT,  K;E FEEL THAT WE CAN APPLY THE
 9       RESOURCES OF THE REPOSITORY THAT WE OPERATE AT
10       EMSL-CINCINNATI AND PROVIDE SURROGATE STANDARDS AND
11       A QC SYSTEM THAT COULD BE STANDARDIZED AND USED TO
12       PRODUCE QUALITY DATA,   THE PC OVERHEAD IS LIMITED TO
13       PROBLEM SAMPLES, WHETHER IT IS 15 PERCENT OF THE
14       SAMPLES, OR 30 PERCENT, OR WHATEVER FIGURE IS DEEMED
15       APPROPRIATE,  ACTIONS  ARE TAKEN IF SURROGATE SPIKE
16       RECOVERIES ARE NOT MET, AND THE DATA FOR SAMPLES
17       THAT THE METHOD WORKS  FOR FROM OUR SURROGATE POINT
18       OF VIEW COULD BE ACCEPTED AS IS,
19
20
21
22
23
24
25
                                  220

-------
 1                       QUESTION AND ANSWER
 2                             SESSION
 3
 4                                MR, DAVIS:  ABE DAVIS,
 5       HOOKER CHEMICAL,  I WOULD JUST LIKE A SIMPLE
 6       EXPLANATION SO I KNOW I AM ON THE SAME WAVELENGTH
 7       AS YOU ARE,
 8            WOULD YOU DEFINE THE DIFFERENCE IN YOUR
 9       TERMINOLOGY BETWEEN SPIKE, SURROGATE SPIKE AND
10       INTERNAL STANDARD?  DURING YOUR TALK I SEEMED TO JUMP
11       BACK AND FORTH AND I'M NOT SURE I KNOW THE DIFFERENCE,
12                                MR, LONGBOTTOM:  WE HAD THAT
13       PROBLEM IN OUR LABORATORY WITH THE DEVELOPMENT OF
14       THE USE OF THE SURROGATE SPIKE,  IN FACT, WHEN WE
15       PUT OUT THE ORIGINAL PURGE AND TRAP, IT WAS OUR
16       INTENTION TO USE BROMOCHLOROMETHANE, 2-BROMO-l-
17       CHLOROPROPANE AND 1,^-DICHLOROBUTANE AS SURROGATE
18       SPIKES, BUT WE DIDN'T USE THAT TERM AT THAT TIME, SO
19       WE CALLED THEM  INTERNAL STANDARDS AND THEY HAVE BEEN
20       ADOPTED AS INTERNAL STANDARDS,
21            AN INTERNAL STANDARD FROM THE PURGE AND TRAP
22       PERSPECTIVE WOULD BE THE TRADITIONAL INTERNAL STANDARD
23       THAT IS USED FOR A FULL METHOD, THAT IS, WHERE YOU
24       CORRECT YOUR RESULTS ON YOUR RECOVERY,  AN INTERNAL
25       STANDARD FOR THE METHOD 625 WOULD BE ONE THAT IS
                                   221

-------
 1       ADDED RIGHT BEFORE til/!T> ANALYSIS TO BE USED AS AN
 2       INSTRUMENT CALIBRATION DEVICE,  A SURROGATE SPIKE
 3       CURRENTLY DOESN'T SERVE ANY PURPOSE IN THE PURGE
 4       AND TRAP  BECAUSE THEY ARE ADDED AT THE SAME TIME
 5       AS  INTERNAL STANDARDS IN COMMON PRACTICE,   IF
 6       YOU ARE GOING TO SPIKE SOMETHING., YOU MIGHT AS WELL
 7       SPIKE AN  INTERNAL STANDARD,   IN METHOD  625,
 8       THE SURROGATE SPIKE WOULD BE A COMPOUND THAT IS ADDED
 9       BEFORE EXTRACTION TO CHECK ON THE APPLICABILITY OF THE
10       METHOD TO THE MATRIX AND THE PERFORMANCE OF THE
11       OPERATOR,
12            WAS  THERE ANOTHER TERM?
13                                MR, DAVIS:   JUST STRAIGHT
14       SPIKES,
15                                MR, LONGBOTTOM:  As WE ARE USING
16       IT  AS THE  ADDITION OF ANY OF THOSE INTERNAL STANDARDS,
17       SURROGATE SPIKES, PRIORITY POLLUTANTS IN A MINIMUM
18       VOLUME OF SOLVENT, TYPICALLY 20 MICROLITERS, BEFORE
19       GC/MS OR  BEFORE ANALYSIS; THAT IS, COMPOUNDS THAT ARE
20       ARTIFICIALLY ADDED,
21                                MR, DAVIS:   You ARE NOT
22       DEFINING  SPIKE AS SIMPLY A COMPOUND THAT YOU ARE LOOKING
23       FOR,   IN A PRIORITY POLLUTANT, THAT COULD ALSO BE AN
24       ADDITION  OF THE SURROGATE SPIKE,  THEN?
25                                MR, LONGBOTTOM:  YES, IT WOULD
                                    222

-------
1       BE A SURROGATE SPIKE, AN INTERNAL STANDARD SPIKE,
2                                MR, DAVIS:  So SPIKE WOULD
3       THEN INCLUDE ALSO THE UNIVERSAL SPIKE AND UNIVERSAL
4       SURROGATE SPIKES, THE OTHER IS NOT,,,
5                                MR, LONGBOW!:  YES,
e                                MR, SPRAGGINS:  BOB SPRAGGINS,
7      RADIAN,  I WOULD LIKE TO SHARE WITH YOU A FEW OF MY
8      OBSERVATIONS,  FOR OVER A YEAR I PERSONALLY RAN THE
9      PURGE AND TRAP DEVICE AT RADIAN, AND THERE WERE CERTAIN
10      THINGS THAT WE FOUND OUT ABOUT THE METHODOLOGY,
11      SINCE THAT TIME WE HAVE TRIED TO INCORPORATE  IN OUR
12      OWN WORK  SOME INTERNAL QUALITY ASSURANCE PROGRAMS,
13      ONE OF THE CRITERIA WE LIKE TO USE IS THAT THE FIRST
14      INTERNAL STANDARD CONTAIN AT LEAST 4,000 AREA COUNTS
15      SO THAT WE GET A REASONABLE AREA COUNT  FOR THE SECOND
16      INTERNAL STANDARD,  THIS AREA RATIO,  IF YOU WILL,
17      BETWEEN THE  TWO, WE HAVE OBSERVED, DEPENDING  ON
18      PURGING EFFICIENCY OF THE SAMPLE, CAN  RANGE ANYWHERE
19      FROM ABOUT 2.7 UP TO ABOUT  4, AND  GENERALLY  IT  IS
20      AROUND 2 AND A HALF, 2.7, WHATEVER,
21            IN THE  BEGINNING WE WORRIED  IF  WE  WEREN'T  REAL
22      CLOSE  TO THAT PURGING EFFICIENCY,  BUT BY RUNNING
23      STANDARDS WE FOUND OUT  THAT IT  REALLY DIDN'T  MATTER
24      TOO MUCH  IF  WE WERE  AT  4, OR MAYBE A LITTLE  OVER  4;
25      WE  STILL, BY RUNNING STANDARDS,  COULD CALIBRATE  VERY
                                  223.

-------
 1      NICELY,  THE  PROBLEM  COMES  IN WHEN YOU STICK THE



 2      SURROGATES  IN  THE  SAMPLE  AT 100 PPB,   IF YOU HAVE ANY



 3      KIND OF CONTAMINATION IN  THE SAMPLE AT ALL, AND THAT IS,



 4      AFTER ALL, WHAT WE  ARE TRYING TO DO, WE ARE TRYING TO



 5      MEASURE SAMPLE CONTAMINATES, NOT SURROGATES, YOU END



 6      UP WITH ABOUT  FOUR COMPOUNDS THAT ELUTE IN THE MIDDLE



 7      OF THE CHROMATOGRAM,  BENZENE, TRICHLOROETHYLENE, D6



 8      BENZENE, AND   DIFLUOROTETRACHLOROETHANE, AND IF THEY



 9      ARE ALL IN  THERE AT AROUND  100PPB, THEN YOU ARE



10      GOING TO HAVE  A  SATURATED SYSTEM ON A HEWLETT-PACKARD



11      MACHINE, AND  YOU ARE  GOING  TO HAVE PROBLEMS ANALYZING



12      THAT SAMPLE.



13           SO WHAT  MY  OPERATORS HAVE HAD TO DO IS LOWER



14      THEIR GAIN  TO  AROUND  TWO  2,500  AREA COUNTS TO COMPLY



15      WITH THE ADDING  OF THE SURROGATES TO KEEP THE THINGS



16      ON SCALE.   WHAT  THIS  DOES is LOWER THE DETECTION



17      CAPABILITY  FOR SOME OF THE  PRIORITY POLLUTANTS,  SOME



18      OF THEM ARE 50 TO.  100 TIMES POORER THAN THE BEST



19      RESPONDERS,   I AGREE  WITH YOU WHOLEHEARTEDLY THAT



20      AN AREA COUNT, YOU SHOULD KEEP TRACK OF YOUR AREA



21      COUNTS ON YOUR INTERNAL STANDARDS, AND WE TRY TO



22      DO THAT,  IF  THERE IS SOMETHING FISHY FROM ONE RUN



23      TO THE NEXT,  WE  WANT  TO KNOW ABOUT IT SO WE KEEP A



24      HANDLE ON IT,  AND  THIS IS PROBABLY A GOOD CRITERIA



25      TO USE,   I  THINK WE DO HAVE A LITTLE BIT OF A PROBLEM
                                  224

-------
 1      WITH SURROGATES  IN  THE  VOAs  AT  100  PPB,
 2                                MR,  LONGBOTTOM:   You  WOULD
 3      SUGGEST A  LOWER  CONCENTRATION,
 4                                MR.  SPRAGGINS:   I  THINK  so,
 5      YES,
 e                                MR,  STANKO:  GEORGE STANKO
 7      WITH SHELL DEVELOPMENT,   THIS is  NOT  REALLY A  QUESTION
 8      OR A CRITICISM,   I  THINK  MANY OF  US FEEL  THAT  THERE ARE
 9      SOME PROBLEMS  IN THE WAY  PEOPLE ARE USING THE  KUDERNA-
10      DANISH EVAPORATOR.  WE  HAVE  NOTICED IN  EVALUATING
11      OUR DATA CERTAIN WAYS TO  SORT OF  GIVE US  A WARM FEELING,
12      I AM NOT SAYING  THIS  IS AN ABSOLUTE WAY OF EVALUATING
13      WHETHER THE  EVAPORATION STUFF WAS DONE  PROPERLY,  BUT  IT
14      SORT OF GIVES  YOU A WARM  FEELING  THAT WHEN YOU FIND
15      TOLUENE'IN YOUR  VOA ANALYSES OF AN  ENVIRONMENTAL
16      SAMPLE, AND  THEN WHEN YOU GO THROUGH  YOUR BASE/
17      NEUTRAL EXTRACTION  AND  ARE ABLE TO  DETECT TOLUENE
18      IN THE BASE/NEUTRAL EXTRACT,  WE FEEL  THAT THE  CHANCES'
19      OF OVERHEATING OR OVERSTRIPPING OF  THE  ENVIRONMENTAL
20      POLLUTANTS,  IT PROBABLY DID  NOT HAPPEN,   IN OTHER  WORDS,
21      WE THINK THIS  MAY BE ONE  PROCEDURE  THAT OUGHT  TO  BE
22      CONSIDERED AS  AN INDICATION  OF  WHETHER  YOU ARE TAKING
23      YOUR EXTRACT DOWN TOO FAR, OVERHEATING  IT,  OR  THE
24      POSSIBILITY  OF LOSING PRIORITY  POLLUTANTS,
25           THIS  IS JUST AS A  SUGGESTION THAT  MIGHT BE TRIED,

-------
 i                                MR,  LONGBOTTOM:   WE WERE LOOKING



 2      AT THE DEUTERATED  DICHLOROBENZENE,WHICH IS AVAILABLE



 3      AND  IS BEING  USED  BY  SOME OF  THE LABORATORIES NOW, BEING



 4      THE  EARLIEST  ELUTER,   MOST VOLATILE OF THE PRIORITY



 5      POLLUTANTS, AND  I  THINK  TOLUENE WOULD BE  VERY APPROPRIATE



 6      ALSO,



 7                                MR,  KLEOBFER:  BOB KLEOBFER,



 8      EPA,  JlM,  I  AM  SORT  OF  UNEASY  ABOUT YOUR APPROACH



 9      OF SELECTING  THE COMPOUNDS THAT ARE MOST  DIFFICULT TO



10      DOAND COMING  UP  WITH  YOUR PERFORMANCE CRITERIA,  BECAUSE



11      IF YOU JUST LOOK AT SOME OF THE DATA THAT I HAVE



12      GATHERED OUT  OF  THE BASE/NEUTRAL FRACTION JUST AS AN



13      EXAMPLE.   IF  YOU TAKE THE WORST CASE, WHICH IS



14      DECAFLUOROBIPHENYL,   WHICH IS 39 PLUS OR  MINUS 18



15      FOR  ONE STANDARD DEVIATION, AND IF YOU APPLY THE



16      USUAL CRITERIA,  WHICH IS THREE  SIGMA, TO  THAT WORST



17      CASE SITUATION,THAT ALLOWS YOU  A RECOVERY BETWEEN



18      MINUS 15 PERCENT UP TO 93 PERCENT AS BEING ACCEPTABLE,



19      AND  OF COURSE THAT IS A  WIDE  ENOUGH RANGE, YOU CAN



20      DRIVE A TRUCK THROUGH,



21           ON THE OTHER  HAND,  IF YOU  SELECT A COMPOUND THAT



22      IS EASIER  TO  DO  SUCH  AS  THE  2'FLUOROBIPHENYL,  YOUR



23      RANGE IS MUCH LESSJ IN THAT CASE IT IS 48 TO 78, BASED



24      ON THREE SIGMA,  IT JUST SEEMS  TO ME THAT YOU REALLY



25      HAVE TIGHTER  CONTROL  OVER THE SITUATION IF YOU SELECT
                                 226

-------
 1       COMPOUNDS WHICH ARE EASIER TO DO,
 2                                MR, LONGBOTTQM:  I PROPOSED
 3       THAT THE PERCENTAGE OF OUTLIERS BE YOUR QUALITY CONTROL
 4       AND SUGGESTED THAT WE COULD ARBITRARILY SELECT WHAT
 5       WE WANTED, WE COULD THROW OUT 15 PERCENT,  IF WE
 6       CONCENTRATE ON 1 PERCENT OUTLIERS, WE WOULDN'T FIND
 7       VERY MANYj THE RANGE FOR ACCEPTANCE WOULD BE TOO WIDE,
 s       HOWEVER, IF WE BACKED THAT OFF TO CRITERIA THAT
                                                        \
 9       ALLOWED FOR MORE WORK, 15 PERCENT, 20 PERCENT, AND
10       CONCENTRATED ON THOSE, I THINK OUR CRITERIA WOULD BE
11       MUCH TIGHTER,
12                                MR, KLEOBFER:  So YOU ARE
13       SUGGESTING THAT WE USE SOMETHING LESS THAN THREE
14       SIGMA FOR THE CRITERIA, THEN,
15                                MR, LONGBOTTOM:  THIS is WHAT
is       DEAN AND PRISCILLA HAVE BEEN STRUGGLING WITH—FINDING
17       ACCEPTANCE LIMITS THAT MAKE SENSE TO THEM, AND THEY
18       WANT TO INTUITIVELY THROW OUT THESE OUTLIERS AND PUT
19       THE GOOD DATA INTO A SEPARATE CASE,  I'M NOT;SURE THAT
20       I AM EXPLAINING IT ANY BETTER THAN IT WAS EXPLAINED
21       YESTERDAY, BUT NO, I AM NOT HAPPY WITH THE THREE SIGMA,
22       I AM NOT HAPPY WITH THE DATA WE GENERATE WITH THE
23       THREE SIGMA, THE PERFORMANCE CRITERIA, AND WHAT I'D
24       LIKE TO DO IS BACK OFF WITH A HIGHER PERCENTAGE,
25       TIGHTER REINS, AND FIND OUT WHAT IN THE WORLD IS GOING
        ON WITH THOSE OUTLIERS, IMMEDIATELY, AS PART OF THE
   	227	

-------
 1      METHOD,
 2                                MR,  SPRAGGINS:  BOB SPRAGGINS,
 3      RADIAN,   JIM.  YOU  SAID  EARLIER THAT IF YOU TRIED TO
 4      RECALCULATE  SAMPLES  BASED UPON SURROGATES RATHER THAN
 5      THE  INTERNAL STANDARDS,  IT DID NOT HELP MATTERS,
 6                                MR,  LONGBOTTOM:  IT WOULD HAVE
 7      HELPED MATTERS HAD THE  SAME MATHEMATICS BEEN APPLIED
 s      THAT BRUCE COLBY APPLIES,
 9                                MR,  SPRAGGINS:  OKAY,  BECAUSE
10      IT SEEMED LIKE IF  YOU PUT TWO DIFFERENT COMPOUNDS IN
11      AND  SAY  YOU  PUT 100  PPB  OF 05  BENZENE, AND YOU MEASURED
12      100  PPB  OF 05  BENZENE  AND THEN YOU MEASURED FIVE TIMES
13      AS MUCH  TRICHLOROETHYLENE AS  YOU SAID YOU PUT IN OR
14      WHATEVER, THAT MAYBE THAT FIVE TIMES AS MUCH WOULD NOT
15      BE AN OUTLIER THEN BECAUSE YOU HAD A GOOD FIX ON YOUR
16      SURROGATE, BUT IF  INDEED YOU  MEASURED FIVE TIMES AS
17      MUCH OF  THE  SURROGATE ALSO, AND YOU RATIOED THIS BACK
18      TO 100 OR WHATEVER,  THEN YOU  SHOULD COME UP WITH A
19      REASONABLE NUMBER  FOR YOUR PRIORITY POLLUTANT SPIKE,
20      IS THIS  NOT  CORRECT?
21                                MR,  LONGBOTTOM:  YES,   I DID
22      THIS WITH A  HAND CALCULATOR AND I COULD NOT FACTOR IN
23      ALL  THOSE FORMULAS THAT BRUCE USED TO RESOLVE OUT AND
24      COME UP  WITH THE TYPE OF CORRELATIONS THAT BRUCE
25      HAS  BEEN DEMONSTRATING,
                                  .223.

-------
                                MR, SPRAGGINS:  WE HAVE DONE
2      SEVERAL THINGS WITH OUR PURGE AND TRAP DEVICE, ONE OF
3      THEM IS AMBIENT AIR MONITORING,  WE TAKE THE LITTLE TUBE
4      OUT TO THE FIELD AND PULL OR PUCH AN AIR SAMPLE
5      THROUGH IT AND MEASURE BENZENE LEVELS OR WHATEVER,
6      AND WE HAVE DONE  WHAT I THINK ARE SOME FAIRLY INTERESTINC
7      STUDIES WHERE WE PUT AN INTERNAL STANDARD ON IN THE
8      FIELD, AND BRING IT BACK IN, AND PUT ANOTHER ONE ON
9      RIGHT AS  IT GOES INTO THE INSTRUMENT,  WE HAVE ALSO
10      DONE SOME OF THIS IN WATER  STUDIES, AND I AM SURPRISED
11      AT GENERALLY THE GOOD EFFICIENCY OF GETTING THE
12      MATERIAL  BOTH ON THE COLUMN OF THE TRAP AND OFF, BUT
13      THIS IS A LIMITED STUDY AND I DO NOT WANT TO BACK  IT
14      UP WITH ANY NUMBERS,
15                               MR, TELLIARD:  THANKS, JIM,
16      OUR NEXT  SPEAKER IS MlKE CARTER,  MlKE  IS GOING TO
17      TALK TO YOU ABOUT SOMETHING COMPLETELY  DIFFERENT CALLED
18      METALS; THESE ARE THE HARD  CHUNKS,
19
20
21
22
23
24
25
                                   229

-------
230

-------
                   PROTON INDUCED X-RAY EMISSION
 2                        ELEMENTAL ANALYSIS
 3
                       BY:  MIKE CARTER
                            GEORGE (IRANI
 5
                                 MR, CARTER:  THE INSTRUMENTAL
 7 i      TECHNIQUE THAT IS ON THE AGENDA, WHICH I UNDERSTAND
 8       FEW PEOPLE HAVE A COPY OF, IS PROTON INDUCED X-RAY
 9       EMISSION,  OUR INTEREST IN THIS ANALYTICAL MEASUREMENT
10       IS BASED ON THE FACT THAT A LOT OF OUR SAMPLES FOR
11       ELEMENTAL ANALYSIS HAVE AN INSOLUBLE RESIDUE, EVEN
12       AFTER THE STANDARD METHODS FOR SAMPLE DIGESTION, AND
13       WE ARE INTERESTED IN KNOWING SOMETHING ABOUT WHAT
14       IS IN THAT SOLID RESIDUE.   PlXE HAS THE CAPABILITY
15       TO LOOK AT SOLID SAMPLES,  AND AS A LITTLE EXTRA
16       BENEFIT, IT ALSO HAS GOOD PERFORMANCE ON SOME OF THE
17       METALS THAT ARE PROBLEM METALS FOR AA AND IfP METHODS,
18       IT IS A METHOD THAT GIVES US GOOD SENSITIVITY,  IT IS
19       A SURVEY TECHNIQUE; IT LOOKS AT A LOT OF METALS AT ONE
20       SHOT, SO THE COST PER DETERMINATION IS QUITE REASONABLE.
21            THE LABORATORY DOING THIS WORK FOR US FOLLOWS THE
22       STANDARD ClNCINNATI-TYPE SAMPLE PREP TECHNIQUES,'
23       THEY ANALYZE THE DIGESTATE AND ANY RESIDUE THAT
24       REMAINS, AND WE GET AN IDEA OF HOW SOME OF THESE
25       ELEMENTS ARE BEING DISTRIBUTED BETWEEN THE DIGESTATE
                                 .211

-------
 1      AND ANY RESIDUE.
 2           So  WITH THAT BACKGROUND I  AM GOING TO TURN THE
 3      REST OF THE PRESENTATION  OVER TO DR,  GEORGE GRANT,  WHO
 4      is WITH THE VIRGINIA  ASSOCIATED  RESEARCH CAMPUS UP
 5      THE ROAD IN NEWPORT NEWS,  VIRGINIA,
 6                                DR,  GRANT:  THANK YOU, MIKE.
 7      OUR LABORATORY'S  MAIN STRENGTH is IN  TRACE ELEMENT
 8      ANALYSES,  WE HAVE THREE  TECHNIQUES,  WE HAVE PIXE
 9      (PROTON  INDUCED  X-RAY  EMISSION), WE HAVE GRAPHITE FURNACE
10      AA CAPABILITY AND  SELECTIVE ION ELECTRODES,  ALL OF
11      YOU DOING METALS  WORK,I AM SURE,ARE FAMILIAR WITH AA,
12      so I WON'T SAY  MUCH ABOUT THAT THIS MORNING,  HOWEVER,
13      I WOULD LIKE TO DO TWO THINGS; I WOULD LIKE TO DESCRIBE
14      HOW THE TECHNIQUE IS  PERFORMED,  GIVE  YOU SOME IDEA
15      OF THE  KIND OF  CAPABILITY WE  HAVE AND POINT OUT A
16      COUPLE  OF AREAS WHERE WE  DO,  I THINK, HAVE THE
17      CAPABILITY OF PROVIDING  INFORMATION COMPLEMENTARY TO
18      THE ANALYSES NOW  BEING PERFORMED BY AA OR ICAP ON
19      THESE SAMPLES,
20            IF I COULD HAVE  SLIDE ONE,  PLEASE.   THE
21      BASIC HEART OF  THE TECHNIQUE  IS  THE VAN DE GRAAF
22      ACCELERATOR WHICH ACCELERATES PARTICLES,  WE USE A
23      PROTON  BEAM AT  AN ENERGY  OF ABOUT 3,8 f1EV,  THE PROTON
24      BEAM COMES DOWN THE CHAMBER HERE, IT IS A VACUUM SYSTEMj
25      IT GOES THROUGH A WINDOW  WHICH PROVIDES ISOLATION
                                 232

-------
PUMPING
STATION
                              4 MeV
                          VAN DE  GRAAFF
                              GENERATOR
                          BENDING  MAGNET
                        — FOCUSING   MAGNETS
                       «J
                         -SCATTERING  CHAMBER
                              (NOT USED)
PUMPING	
STATION
KAPTON WINDOW-

X-RAY  DETECTOR-
FILTER SYSTEM
ROTATING
    TARGET
-CM
           DRIVE
           "MOTOR
 TARGET
"CHAMBER
 ( He FILLED)
                        BEAM  STOP
                           232A

-------
 1
         BETWEEN THE VACUUM SYSTEM INTO THE SAMPLE COMPART-
 2
         MENT,   THIS IS A TOP VIEW OF THE SYSTEM, X-RAYS
 3
         EMITTED OR GO THROUGH A FILTER SYSTEM HERE INTO
 4
         A LITHIUM-DRIFTED SILICON DETECTOR,  THE FILTER
 5
         SYSTEM VARIES FROM INSTALLATION TO INSTALLATION,
 6
         VIE HAVE DELIBERATELY CONSTRUCTED A FILTER WHICH
 7
         ATTENUATES THE LIGHTER X-RAYS FROM MORE ABUNDANT
 8
         ELEMENTS SUCH AS MAGNESIUM,  ALUMINUM AND SO FORTH,
 9
         IN ORDER TO ENHANCE OUR CAPABILITY FOR TRANSITION
10
         ELEMENTS AT A MID-RANGE AND HEAVIER ELEMENTS,   IN
11
         OTHER  WORDS, WE HAVE OPTIMIZED OUR SYSTEM FOR FIRST-
12
         ROW TRANSITION ELEMENTS AND HEAVIER,
13
            SLIDE 2, PLEASE.  THIS is A PICTURE OF THE SYSTEM,
14
         OBVIOUSLY IT is NOT A BENCH-TOP MODEL,  THE ACCEL-
IB
         ERATOR HERE IS FILLED WITH SULFUR HEXAFLUORIDE
16
         AS A DIELECTRIC GAS,   THE SAMPLE COMPARTMENT IS
17
         RIGHT  UP IN HERE,
18
            SLIDE 3, PLEASE.  THIS is A SCHEMATIC OF THE
19
         SYSTEM,   ON THE LEFT-HAND SIDE WE SEE THE TYPE
20
         OF SAMPLE ARRANGEMENT WE HAVE,  THIS  CONSISTS OF A
21
         TRAY THAT IS APPROXIMATELY THREE FEET LONG, CONTAIN-
22
         ING 11 COMPARTMENTS UPON WHICH WE INSTALL THE SAMPLES
23
         THAT ARE PREPARED IN THE ANALYTICAL LAB,  I THINK, IF
24
25        YOU CAN REMEMBER IN THAT PREVIOUS SLIDE, THAT THAT IS
                                 233

-------
233A

-------
                   2nd Detector
                            To Shielded Beam Dump
                          SCHEMATIC OF THE CHARGED PARTICLE

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                                       1024
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*(of Data XFR from analyzer
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                                                                              V
                                                                                   Mag. Tape
                                                                             TeleType

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 1      HARDLY A VERY CLEAN  ENVIRONMENT  FOR  TRACE  ELEMENT
 2      ANALYSES,  A.LL OF THESE  SAMPLES  ARE  PREPARED  IN  THE
 3      ANALYTICAL LAB, AND  THE  TARGETS  WERE MADE  FOR  PIXE
 4      ANALYSIS IN A CLEAN  ROOM,   THEY  ARE  INSTALLED  IN
 5      THIS 11-COMPARTMENT  TRAY THAT  IS PUT IN  A  SEALED
 e      PLEXIGLAS  CONTAINER AND THEY  ARE TRANSPORTED  FROM AN
 7      ANALYTICAL LAB TO THE ACCELERATOR THROUGH  THAT,  THEY
 8      ARE ONLY OPEN FOR A  BRIEF  INSTANT WHILE  THE TRAY IS
 9      BEING  INSERTED IN THE SAMPLE COMPARTMENT,
10          INSTEAD OF RUNNING SAMPLES  UNDER  HIGH VACUUM,
11      WE  RUN THEM  IN APPROXIMATELY 109 MILLIMETERS OF  HELIUM
12      AND WE ROTATE THE SAMPLES,  WHICH IS  A LITTLE DIFFERENT
13      FROM WHAT MOST PEOPLE DO WITH  PIXE.
14           THE ADVANTAGES  OF THIS TECHNIQUE ARE  THAT THE
15      HELIUM PROVIDES COOLING,  THE  ROTATION OF  THE  TARGET
16      ALSO PROVIDES COOLING, ALLOWING  US TO USE  HIGHER BEAM
17      CURRENTS AND  INCREASE OUR  SENSITIVITY,   So WE  HAVE,
18      I THINK, EXCELLENT  SENSITIVITY FOR ALL THE ELEMENTS  •
19      ACROSS THE SPECTRUM,  WHILE THE  PARTICLE BEAM  COMES
20      IN  HERE, THE  X-RAY  IS EMITTED,  THE  DATA IS ACQUIRED
21      BY  1,000 CHANNEL, MULTI-CHANNEL  ANALYZER,  AT  THE
22      PRESENT TIME  THE DATA ARE  DUMPED THROUGH A TELETYPE
23      AND ANALYZED  BY A COMPUTER  OFF-LINE.  WE DO HAVE THIS
24      PDP-11 COMPUTER NOW  AND  THE SOFTWARE IS  BEING  WRITTEN
25      AND DEBUGGED  AND  I  HOPE  IN  A MATTER  OF WEEKS  THAT  WE
                                    234

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 1       WILL  BE  ON-LINE,  ELIMINATING THIS VERY TROUBLESOME




 2       TELETYPE.



 3            IF  I  MIGHT  HAVE SLIDE 4, PLEASE,  THIS IS



 4       AN  EXAMPLE OF  THE DATA AND WHAT WE DO WITH IT,  THOSE



 5       OF  YOU WHO WERE  OVER AT LOCKHART's LAST NIGHT, I WILL



 6       POINT OUT  THAT ALONG WITH YOUR FAVORITE GOLDEN



 7       BEVERAGE,  YOU  GET A LOT OF TRACE ELEMENTS IN YOUR



 s       CLAMS; THAT is WHAT THE SAMPLE WAS IN THIS CASE.   THE



 9       SPECTRUM CONSISTS OF A SET OF MULTIPLET  PEAKS,   IN



10       THIS  CASE  WE USE  INDIUM,TYPICALLY, AS AN INTERNAL



11       STANDARD,   THIS  PEAK,  AND THAT ONE AND THAT ONE  ARE



12       ALL FROM INDIUM  THAT WE ADD IN KNOWN AMOUNTS TO  THE



13       SAMPLE AFTER DIGESTION,   WE HAVE CALIBRATED INTO



14       THE COMPUTER ON  DISC THE  EXPERIMENTAL LINE



15       SHAPES FOR EACH  ELEMENT FROM ALUMINUM THROUGH URANIUM,



16       AND THE  COMPUTER  PROGRAM DECONVOLUTES THE SPECTRUM AND



17       ESTIMATES  THE  PEAK AREAS FOR EACH OF THE MULTIPLETS



18       FOR EACH ELEMENT  PRESENT IN THE SAMPLE, BEGINNING WITH



19       THE MAJOR  PEAKS  AND SEQUENTIALLY SCANNING THROUGH



20       AND PICKING UP THE MINOR PEAKS AS WE GO,



21            THE ANALYSIS I HAVE SHOWN HERE YOU WILL NOTE ON



22       THE LEFT-HAND  SIDE THAT THE Y~AXIS IS LOG OF THE



23       COUNTS PER CHANNEL; IN OTHER WORDS, IT IS A SEMILOGA-



24       RITHMIC  DISPLAY  HERE.   FlRST IS THE X-RAY ENERGY



25       IN  KEY FROM ZERO  TO 40,   THE TRACES I HAVE SHOWN HERE
                                 235

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     AI-ASTARTE (C2)

   Composite  Spectrum
Smooth background and
spectral defects
      Background
    Subtracted. Composite
      Spectrum
    X-Ray Energy (KEV)
         Fig.  I

          235A
j                     '    I
v—FIT (continuous dark line)
   and 'Background, Subtracted Spectrum
   (Indistinguishable from the fit here
   but distinguishable at (T) )

-------
 1      CONSIST  OF  FOUR.   THE  TOP  TRACE  CONSISTS  OF THE RAW  '



 2      DATA WITH A  LINE  DRAWN  THROUGH  THE  THOUSAND  POINTS,



 3      THE NEXT TRACE UNDERNEATH IT, RIGHT  HERE,  CONSISTS OF



 4      THE COMPUTER-CALCULATED BACKGROUNDj  THIS  IS  COMPLETELY



 5      DONE BY THE  COMPUTER,   THE  BOTTOM TWO  TRACES ARE THE



 6      RAW DATA MINUS COMPUTED BACKGROUND  AND ALSO  THE  SUMS



 7      OF THE COMPUTED CURVES  FROM THE DECONVOLUTED DATA,   I



 8      THINK YOU CAN SEE,  IN MOST  CASES  YOU CANNOT  DISTINGUISH



 9      ONE LINE FROM THE OTHER; THEY ARE SUPERIMPOSABLE, WHICH



10      IS AN INDICATION  OF THE QUALITY OF  OUR FIT THROUGH THE



11      DATA,



12           I THINK YOU  CAN SEE HERE,  THIS  PARTICULAR  PEAK  IS



13      THE CADMIUM  YOU ATE, WHICH  IS FAIRLY ABUNDANT IN CLAMS,



14      YOU CAN SEE  THAT  THERE  IS A LITTLE  BIT OF  A



15      DISCREPANCY  HERE  BETWEEN A  FEW  OF THE  DATA POINTS



16      FOR THE RAW  DATA  MINUS  BACKGROUND IN THE  FITTED  PEAK,



17      THE FINAL STEP, AFTER THE DECONVOLUTION IS  FITTED, IS



18      TO COMPUTE THE CONCENTRATION OF EACH COMPONENT  IN



19      THE SAMPLE,  AND THE COMPUTER PROGRAM COMPARES THE



20      COMPUTED CONCENTRATION  TO THE STATISTICAL  PARAMETERS,



21      WE COUPLE IN THE  UNCERTAINTY  IN THE BACKGROUND



22      SUBTRACTION, COMPUTATION, THE STATISTICAL  NOISE



23      WHICH VARIES THROUGHOUT THE SPECTRUM,  AND  SO EACH



24      ELEMENTAL CONCENTRATION ALSO HAS  A  STANDARD



25      DEVIATION COMPUTED  FOR  THAT CONCENTRATION, AND
                                236

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 1      OF COURSE WE  USE  A  TWO  STANDARD DEVIATION  CRITERION



 2      SO THAT ANY COMPUTED  CONCENTRATION  LESS  THAN  TWO



 3      STANDARD DEVIATIONS  IS  REPORTED AS  A  DETECTION  LIMIT



 4      NUMBER,



 5           THAT is  HOW  THE  SYSTEM  is SET  UP,   I  WON'T TALK



 6      ABOUT PRIORITY  POLLUTANT  MEASUREMENTS TODAY BECAUSE,



 7      FOR ONE REASON; WE HAVE  ONLY  RECENTLY  BEGUN MAKING



 8      MEASUREMENTS, BUT I WILL  TELL YOU  INSTEAD  ABOUT A



 9      FAIRLY COMPLETE STUDY WE  HAVE PERFORMED  IN THE  PAST



10      WHICH WAS PERFORMED ON  SEDIMENTS,   THESE ARE  OCEAN



11      SEDIMENTS AND WE  WERE ATTEMPTING TO DETERMINE THE



12      METALS THAT ARE LEACHABLE FROM THE  SEDIMENTS,   THE



13      EXPERIMENTAL  PROCEDURE  WAS A FIVE  NORMAL NITRIC ACID



14      LEACH FOR TWO HOURS AT  ROOM  TEMPERATURE, AND  THEN^



15      WE PERFORMED  A  VARIETY  OF PIXE AND  ATOMIC  ABSORPTION



16      MEASUREMENTS  ON THESE LEACHATES,



17         ON SLIDE 5  IS SHOWN SOME OF THE TYPE OF



18      DATA WE HAD,  THESE  REPRESENT THE  EXTREMES OF



19      BEHAVIOR THAT WE  OBSERVED,   ON THE  TOP TRACE  IS THE



20      PIXE SPECTRUM FOR WHAT  I  AM  CALLING A HIGH CALCIUM



21      SAMPLE,  THIS IS  A  SAMPLE IN WHICH  THERE WAS  A  LOT



22      OF BIOLOGICAL MATERIAL  AND THEREFORE  SKELETAL



23      FRAGMENTS CONTAINING  HIGH CALCIUM,  THESE  ALSO



24      TENDED TO HAVE  LARGE  CONCENTRATIONS OF IRON AND



25      STRONTIUM,, AS YOU CAN SEE FROM THE  SPECTRUM,
                                237

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                            Cd
I I  I I  I I I  I I  I I I  I I I  I I  I I I  I I
        10
       20            30
X-ray  ENERGY (KeV)
                                              (a)
                                                 40
                                             (b)
                        237A

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1           ON THE BOTTOM TRACE IS A SPECTRUM REPRESENTATIVE
2       OF WHAT I CALL A LOW CALCIUM SAMPLE WHICH CONSISTED
3       MAINLY OF SILICA AND INORGANIC COMPONENTS, VERY LITTLE
4       BIOLOGICAL ACTIVITY, AND THEREFORE WAS MUCH LOWER  IN
5      CALCIUM,  NOW, THE APPARENT PEAKS ARE COMPARABLE,
6      YOU WILL SEE HERE IN THIS CASE, BECAUSE WE ARE ABLE
7      TO RUN THE SAMPLE, WHICH WAS LOW IN ABUNDANT ELEMENTS,
8      NAMELY, CALCIUM, FOR A LONGER TIME PERIOD, THUS GETTING
9      BETTER STATISTICS ON THE TRANSITION ELEMENTS IN THIS
10      RANGE HERE.  So WE ARE LIMITED, AS ANYBODY IS IN A
11      SYSTEM FOR THE DYNAMIC RANGE, THE PROBLEM THAT WAS
12      ADDRESSED JUST A MINUTE AGO, WITH TOO MUCH SURROGATE
                                    c
13      SPIKE.  K!E CAN COUNT UP TO 10° COUNTS AND THEN WE
14      HAVE TO STOP, SO IN OUR TECHNIQUE THE PRESENCE
15      OF AN ABUNDANT ELEMENT GIVING US A LARGE PEAK
16      WILL REDUCE THE DETECTION LIMITS FOR ANY OF THE OTHER
17      ELEMENTS PRESENT IN THE SAMPLE,
18          ON SLIDE 6 I HAVE A SET OF TYPICAL ELEMENTS THAT
19      WE FOUND IN THESE SEDIMENT LEACHES,  As I MENTIONED,
20      THE TECHNIQUE GIVES US A VALUE FOR EVERY ELEMENT
21      BETWEEN ALUMINUM AND URANIUM INCLUSIVE,
22          MANY OF THE ELEMENTS ARE TYPICALLY FOUND AS DETECTION
23      LIMIT NUMBERS, SO I HAVE NOT INCLUDED THEM IN THIS
24      SLIDE.  I WOULD ALSO POINT OUT THAT FOR SOME OF THE
25
                                238

-------
     Typical  Marine Sediment Components (pom, dry v;t.)  After 5N
High Calcium Station (A2S3)
Low Calcium Station (CIBI)
Atom i c
Symbol
A!
Si
P
S
Cl
K
Ca
Sc
Ti
- V
Cr
Mn
Fe
Co
NI
Cu
Zn
* *1
Br
. Rb
Sr
Cd
*ln
Sn
Ba
Ce
Hg
Pb

Concentration
516.
Less Than 2SD
Less Than
84.
492.
739.
3.0862
50.7
Less Than 2SD
6.40
1.56
48.8
2241.
5.61
1.88
2.46
11.61
1.14
2.67
1.09
II 1.8
Less Than 2SD
66.8
Less Than 2SD
Less Than 2SD
11.8
Less Than 2SD
6.10
Absolute
Std. Dev.
84.
55.40
19.94
26.
19.
18.
0.058
4.5
0.91
0.92
0.70
1.4
42.
0.92
0.37
0.24
0.34
0.19
0.15
0.10
2.2
0.24
1.3
0.26
1.31
2.6
0.44
0.38
Concentration
(ppm)
47.8
65.6
19.4
189.7
17.63
80.88
580.6
1.07
2.786
1.41!
0.404
24.49
324.2
0.561
0.165
0.234
2.250
0.510
3.049
0.028
3.413
0.096
66.70
0.206
Less Than 2SD
0.83
Less Than 2SD
1.284
Absolute
Std. Dev.
5.0
3.3
3.6
1.7
0.80
0.61
2.3
0.22
0.089
0.088
0.063
0.16
1.3
0.078
0.020
0.014
0.020
0.017
0.023
0.010
0.025
0.034
0.25
0.037
0.28
0.27
0.01
0.031
                                         238A

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 1      ELEMENTS, THE SENSITIVITY  IS RELATIVELY POOR,  FOR




 2      EXAMPLE, ALUMINUM  IS ON THE RAGGED  EDGE; OUR DETECTION



 3      LIMITS ARE NOT GOOD FOR THAT,  SO  GENERALLY  SPEAKING



 4      WE WILL DETERMINE  ALUMINUM BY  ATOMIC ABSORPTION  IF



 5      THAT NUMBER  IS DESIRED,



 6           BUT YOU CAN SEE, ON THE LEFT-HAND SIDE  I  HAVE



 7      THE TYPICAL  CONCENTRATIONS DETERMINABLE IN  A HIGH



 8      CALCIUM STATION, THAT IS, ONE REPRESENTING A  LOT  OF



 9      BIOLOGICAL ACTIVITY, A LOT OF  SKELETAL FRAGMENTS,



10      ET CETERA, AND OVER HERE A LOW CALCIUM STATION,   YOU



11      WILL NOTICE, I HAVE NOT, OF COURSE, ATTEMPTED  TO



12      RESTRICT MY  ELEMENTS TO THE PRIORITY POLLUTANT



13      LIST AND IN  ADDITION TO THE 13 ELEMENTS OF  INTEREST,



14      WE CAN EASILY SEE  A NUMBER OF  OTHER TRANSITION



15      ELEMENTS,  INCLUDING  SOME  HEAVIER  ELEMENTS  THAT ARE



16       COMMONLY  FOUND  IN  ENVIRONMENTAL  SAMPLES,



17           IN OUR  STANDARD DEVIATIONS OVER HERE,  YOU CAN



18      MAKE A ROUGH ESTIMATE OF WHAT  OUR DETECTION  LIMIT



19      WOULD BE IN  THIS TYPE OF SAMPLE BY  JUST DOUBLING



20      THIS 'NUMBER, I ALSO POINT  OUT  THAT  THESE NUMBERS ARE



21       IN PARTS PER MILLION DRY WEIGHT,  THEY ARE  NOT



22      SOLUTION CONCENTRATIONS, AND ALMOST  ALL THE  NUMBERS



23       I AM SHOWING YOU TODAY ARE COMPUTED IN PARTS PER



24      MILLION  DRY WEIGHT,  As YOU ARE  ALL AWARE  IN  DOING



25       I CAP AND AA  MEASUREMENTS,  THE  USUAL DISCUSSION
                                239

-------
TABLE-10 (contd.)

Solution #2
Element

Cr
N!
Cu
Rb
In
Cs
Pb
(Master Mix
Known CONG
(ug/ml )

2.00
5.00
5.00
1.009
25.00
10.28
5.00
Solution
(6166-3)*
1.97
.03
4.89
.03
4.84
.03
0.98
.01
25.0
10.3
.2
4.82
.03
Analyses-PIXE and
PIXE Analysis
(6166-4)*
1.90
.02
4.92
.02
4.83
.02
0.99
.01
25.0
10. 1
.1
4.81
.02
AA)
(6325-3)*
2.06
.02
5.21
.03
5.10
.03
1. 01
.01
25.0
10.3
.1
4.99
.03
239A

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1       OF THE DETECTION LIMITS IS BASED UPON SOLUTION
2       CONCENTRATIONS, AND OF COURSE IN TERMS OF AN
3      INDUSTRIAL EFFLUENT, WHICH IS LIQUID, THAT IS
4      PROBABLY THE MOST RELEVANT VARIABLE.  BUT IN TERMS
5      OF A SOLID SAMPLE, PARTICULATES OR SAMPLE SLUDGES,
6      PARTS PER MILLION DRY WEIGHT IS PROBABLY THE MORE
7      RELEVANT COMPARISON TO MAKE.
8          WE USE A VARIETY OF TECHNIQUES FOR CALIBRATION
9      OF PIXE AND FOR CHECKING OUR QUALITY CONTROL, ONE
10      OF WHICH IS ILLUSTRATED IN SLIDE 7,
11          THESE ARE MASTER MIXES, AND THEY ARE COMPLETELY
12      ANALOGOUS TO THE EPA CHECK SAMPLES,  I DO NOT HAVE
13      A SLIDE OF THE CHECK SAMPLES, BUT WE HAVE ANALYZED
14      SOME AND GET EXCELLENT DETECTION LIMITS AND REPRO-
15      DUCIBILITY FOR THEM,
16          THIS PARTICULAR STUDY WAS DONE OVER A SIX-MONTH
17      PERIOD ON THE SAME SOLUTION,  WE WERE TESTING,
18      REALLY, TWO VARIABLES HERE: THE STABILITY OF THE
19      SOLUTION THAT WE WERE ABLE TO MAKE UP FROM REAGENT
20      GRADE CHEMICALS, AND FURTHERMORE, THE STABILITY OF
21      THE PIXE SYSTEM,  THERE WAS NO RECALIBRATION OF PIXE
22      DURING THIS TIME, THOUGH THESE TWO WERE RUN ON THE
23      SAME DAY, IN THE SAME TRAY, AND THIS LAST ONE WAS
24      RUN SIX MONTHS LATER ON THE SAME SOLUTION, SO ANY
25      DIFFERENCES REFLECT BOTH SOLUTION CHANGES AND PIXE
                                 240

-------
 1       CHANGES,   AS YOU CAN SEE, THE DIFFERENCES ARE VERY



 2       MINOR,



 3           ON  SLIDE 8 WE ARE VERY CONCERNED ABOUT THE



 4       ANALYTES*  STABILITY,  As ANYBODY DOING TRACE ELE-



 5       MENT ANALYSIS IS AWARE, IF YOU ARE USING A SINGLE-



 6       ELEMENT-AT-A-TIME ANALYTICAL METHOD SUCH AS ATOMIC



 7       ABSORPTION,  AND YOU ARE ANALYZING A LARGE NUMBER OF



 8       SAMPLES,  A RUN FOR ONE ELEMENT MAY TAKE YOU FOUR



 9       HOURS,   $0 UNLESS YOU HAVE A LOT OF INSTRUMENTS



10       AVAILABLE TO YOU, THE ANALYSIS FOR A MULTIELEMENT



11       ANALYSIS OF A SAMPLE MAY TAKE SEVERAL DAYS,  WE



12       WERE CONCERNED ABOUT WHETHER THE SAMPLES, ONCE



13       PREPARED IN THE FORM OF AN ANALYTE, WOULD BE STABLE



14       FOR A MUCH LONGER TIME PERIOD THAN WE MIGHT ENCOUNTER



15       IN THE  LAB DURING THAT ANALYSIS,



16           THIS STUDY WAS DONE OVER A THREE-WEEK PERIOD,



17       WHICH FAR EXCEEDED THE TIME THAT WE WOULD BE DOING



18       THE ANALYSIS, WHICH WAS TYPICALLY A COUPLE OF DAYS,



19       THE FOUR REPLICATIONS, THEN, ARE FOUR TARGETS MADE



20       FROM THE SAME SOLUTION FOR THIS PARTICULAR STATION



21       WHICH WAS A LOW CALCIUM STATION WITH LOW BIOLOGICAL



22       ACTIVITY,   EACH PIXE TARGET WAS SPOTTED AND ANALYZED



23       COMPLETELY INDEPENDENTLY OVER A PERIOD OF THREE WEEKS,



24       IF YOU  LOOK AT THE DATA, YOU WILL SEE THAT THERE ARE



25       PRACTICALLY NO CHANGES WHATEVER THAT SHOW A TREND, WITH
                                  .241

-------
             Sediment Leach
Analyte Stab!Iity Study (3 week period)
             Somplo C4-3 (Cruise  I)
Element
CA
Tl
V
CR
MN
FE
CO
N!
CU
ZN
AS
SR
R!
14819
200
45.3
I.I
14.45
.90
6.41
.65
85.6
1.6
3932.
53
9.44
.92
2.70
.29
7.10
.27
23.82
.40
4*18
.20
78.7
I.I
R2
15175
210
49.6
1.2
12.24
.90
4.96
.65
82.3
1.6
3925.
55
8.85
.91
3.14
.24
6.60
.16
25.56
.41
4.14
.20
78.5
I.I
R3
14933
280
44.5
1.5
14.2
1.2
6.98
.84
85.1
2.1
4057.
75
7.2
1.2
2.92
.39
7.13
.37
23.47
.54
4.24
.26
79.5
1.5
R4
15879
310
48.7
1.6
15.9
1.3
8.61
.84
87.6
2.2
4169.
82
6.4
1.2
2. si
.40
6.84
.38
23.60
.57
4.13
.27
79.5
1.6
                                          Mean +  S.D



                                           15202 + 356





                                          47.0 +  1.88





                                           14.2+_ 1.15





                                           6.7 i 1.12





                                          85.1 +  1.64





                                          4021. +86.92





                                           7.9 +_ 1.05





                                          2.89+_ 0.14





                                          6.92 +_ 0.18





                                          24.11 +.0.73






                                          4.175+_ 0.03






                                          78.97 +  0.31
                        241A

-------
 1
        THE POSSIBLE EXCEPTION OF IRON AND COBALT DOWN HERE

        WHICH DID SHOW A SLIGHT TREND,  HOWEVER, IF YOU
 3
        ANALYZE THIS TREND AS A FUNCTION OF TIME. INCLUDING
 4
        THE STATISTICAL UNCERTAINTIES IN EACH OF THOSE NUMBERS,
 5
        YOU FIND THAT THE TREND IS NOT SIGNIFICANT, SO A VERY
 6
        SLIGHT TREND WAS THERE BUT AT A VERY LOW LEVEL OF
 7
        SIGNIFICANCE,
 8
            HAVING SATISFIED OURSELVES THAT THE ANALYTES,
 9
        WITH REAL SAMPLES, WERE STABLE OVER A TIME PERIOD
10
        MUCH LONGER THAN THAT WHICH WE WOULD HAVE IN THE LAB,

        WE FELT COMFORTABLE IN OUR AA DATA,  OF COURSE THE
12
        PIXE TARGETS, WHEN WE DO THOSE MEASUREMENTS, ARE
13
        MADE UP IMMEDIATELY AFTER PREPARATION OF THE ANALYTE,
14
        I  MIGHT DESCRIBE JUST BRIEFLY THE PREPARATION OF
15
        THE TARGETS, THERE ARE TWO TYPES,  IF WE HAVE A SAMPLE
16
        THAT IS SOLUBILIZABLE, SUCH AS AFTER AN ACID DIGES-
17
        TION, THEN WE SPOT THAT SAMPLE,  AFTER DOPING WITH
18
        INDIUM OR ANOTHER SUITABLE INTERNAL STANDARD, ONTO
19
        A  THIN POLYMER FILM THAT WE MAKE IN OUR OWN LAB,   V»E
20
        HAVE BEEN UNABLE TO PURCHASE COMMERCIALLY FILMS THAT
21
        ARE THIN ENOUGH AND CLEAN ENOUGH SIMULTANEOUSLY IN
22
        ORDER TO USE FOR OUR ANALYSIS,  I MIGHT ADD, AS A
23
        BALLPARK FIGURE, OUR TYPICAL PIXE SENSITIVITIES FOR
24
        THE ELEMENTS ACROSS THE PERIODIC TABLE FALL IN THE
25
        RANGE OF ,1 TO 10 NANOGRAMS PER SQUARE CENTIMETER ON

        THE TARGET,
   	242	        	

-------
           NOW, THESE  CAN  BE  INCREASED  BY  RUNNING FOR A
 2
       LONGER TIME  PERIOD  AND GETTING BETTER STATISTICAL
 3
       PRECISION, BUT  THAT IS A  REASONABLE WORKING NUMBER,

           THE  FIRST TYPE  OF  TARGET WE  MAKE IS  FROM A

       SOLUBLE  SAMPLE,   WE DOPE  THAT INTERNALLY,  SPOT IT
 6
       ON A TARGET  AND IT  IS  DRIED  IN AN  INFRARED OVEN

       IN THE CLEAN ROOM,   ONCE  THE SAMPLE IS DRIED,  WHICH
 8
       TAKES A  MATTER  OF A FEW HOURS, THESE TARGETS,  IF
 9
       THEY ARE NOT RUN  IMMEDIATELY ON  THE ACCELERATOR,
10
       ARE STORED  IN SEALED PLASTIC TRAYSj THEY ARE STABLE

       INDEFINITELY IN THAT WAY,

           THE  OTHER TYPE  OF  TARGET THAT WE CAN DO,  AND I

       THINK IT MAY REPRESENT A  LITTLE  BIT DIFFERENT  CAPA-
14
       BILITY THAN  YOU HAVE WITH ICAP OR AA,  IS A POWDER
15               ..
       TARGET,  WE  ARE ABLE TO ANALYZE  SOLID SAMPLES,

       WE HAVE  USED, FOR EXAMPLE, POWDERED BOVINE LIVER,
17
       ORCHARD  LEAVES, NBS PINE  NEEDLES AND SO  FORTH  AS
18
       CALIBRATION  CHECKS;  IN FACT, WE  HAVE EVEN  DONE A
19
       STUDY OF TRACE  ELEMENT UPTAKE IN PINE TREES BASED
20
       ON ANALYSIS  OF  THE  POWDERED  PINE NEEDLE  SAMPLE,
21
       WE CAN ANALYZE  THESE WITHOUT DOING  A DIGESTION,
22
       THE RESTRICTION IS  THAT THE  THICKNESS OF THE POWDERED
23
       SAMPLE OR SOLID SAMPLE ON THE TARGET MUST  BE THIN
24
       ENOUGH THAT  X-RAY ATTENUATIONS ARE  INSIGNIFICANT,
25
       WE ALSO  DO HAVE A METHOD  FOR CORRECTING  FOR X-RAY
                                 243

-------
 1       ATTENUATION,  BUT  WE  PREFER,  IF AT ALL POSSIBLE, TO

 2       MAKE  THE  LAYER  THIN  ENOUGH  THAT WE DO NOT HAVE TO DO

 3       THAT  CORRECTION,   THOSE  ARE  THE TWO GENERAL TYPES OF

        TARGETS THAT  WE DO,

 5           IF  I  COULD  HAVE  SLIDE 9,  PLEASE,   I  KNOW THIS

 6       IS  NOT A  GOOD SLIDE  BECAUSE  THERE IS  TOO MUCH

        INFORMATION ON  IT,   I  DID WANT TO SHOW YOU THE

 8       STATISTICAL APPROACH,  THIS  STUDY WAS DONE IN ORDER

        TO  TEST THE COMPARABILITY OF THE MEASUREMENTS FOR
10
        THESE PARTICULAR  ELEMENTS THAT WE WERE LOOKING AT

        BY  ATOMIC ABSORPTION AND BY  PIXE.   IN OTHER WORDS,

12       WE  WANTED TO  SHOW EXACTLY HOW COMPARABLE THE DATA

        WOULD BE  IF WE  LOOKED  AT IT  BY ONLY ONE  OF THE

        ANALYTICAL METHODS,  SO WE WANTED TO DO A STATISTICAL

        ANALYSIS,  WE PERFORMED  PIXE AND ATOMIC  ABSORPTION
1 fi
        ANALYSES  FOR  SEVEN ELEMENTS  ON APPROXIMATELY 144
17
        SEDIMENT  LEACHATES OF  VARIOUS TYPES,  AND WE EVALUATED
18
        THE DATA  IN THIS  WAY,  THIS  IS ONLY PART OF THE DATA,
19           T
            I MIGHT ADD THAT ONE OTHER THING  WE  WERE
20
        INVESTIGATING AT  THIS  POINT  WAS SAMPLING

        VARIABILITY,  NUMBERS  ONE THROUGH SIX HERE REFLECT
22
        SIX GRAB  SAMPLES  TAKEN AT THE SAME SITE, AT THE
23
        SAME TIME, AND  FOLDED  INTO  THE DIFFERENCES BETWEEN
24
        THESE NUMBERS,  THEN, IS  SAMPLING VARIABILITY AS
25
        WELL AS ANALYTICAL VARIABILITY,  B~l AND B~2 WERE

-------
                              TABLE V - PIXE/AA Ratio for 5N HNO^ Sediment Leachates
«
Sample
1
2
3
4
5
6
Bl
B2
SB
Mean Rata
_* S.D^
Cr
2.2 * .5
2.63 * .03
=0.84 * .21
3.6 ± .5
2.71 * .07
=1.33 * .18
3.5 * .4
2.59 * .07
=1.35 * .19
2.7 * .4
2.47 * ..05
=1.09 * .17
b
2.67 * .12
2.8 * .4
2.36 * .03
=1.19 * .19
2.9 * .4
2.54 * .03
=1.14 * .17
2.5 * .4
2.50 * .06
=1.00 * .17
2.1 * .4
2.2 * .1
=0.95 * .20
° 1.11 * .18
Fe
930 * 21
924 * 60
= 1.01 *-.07
896 * 23
904 ± 59
=0.99 ±.07
897 ± 20
900 * 59
=1.00 ±.07
800 ± 15
826 ± 58
=0.97 ±.07
962 ± 17
941 ± 57
=1.02 ±.06
728 ± 16
796 ± 57
=0.92 ±.08
815 ± 18
847 * 58
=0.96 ±.07
766 ± 16
849 * 58
=0.90 ±.06
870 * 10
781 * 39
=1.11 *.06
0.99 ±.06
Ni
1.0 ± .2
1.3 ± .3
=0.77 ± .26
0.7 ± .2
1.2 ± .3
=0.58 ± .24
0.9 ± .2
1.2 ± .3
=0.75 i .24
1.0 ± .2
1.0 ± .4
=1.00 ± .45
0.8 ± .2
1.2 * .3
=0.67 ± .26
1.1 * .2
1.0 ± .3
=1.10 ± .39
1.1 * .2
1.1 * .3
=1.00 * .36
1.0 ± .2
1.2 * .2
=0.83 ± .26
1.0 * .2
0.9 * .3
=1.11 * .43
0.87 ± .19
Cu
0.77 * .15
0.71 * .02
=1.08 * .21
0.48 ± .14
0.60 ± .02
=0.81 ± .24
0.50 ± .11
0.57 ± .04
=0.88 ± .22
0.41 ± .10
0.51 ± .05
=0.81 ± .21
0.66 ± .1
0.61 ± .05
=1.08 ± .19
0.67 ± .12
0.59 ± .02
=1.14 ± .22
0.81 ± .11
0.62 * .01
=1.32 ± .18
0.58 ± .13
0.57 * .02
=1.02 ± .23
0.85 * .12
0.58 * .02
=1.46 * .22
1.07 ± .22
Zn
6..6 * .2
6.3 ± .1
=1.05± .04
6.0 ± .2
5.8 ± .3
=1.04± .04
5.7 * .2
5.5 ± .1
=1.04± .04
5.4 ± .1
5.1 ± .1
=1.06± .03
6.6 ± .2
5.7 ± .2
=1.17± .06
5.2 ± .2
5.1 ± .2
=1.02± .06
6.1 ± .2
5.9 ± .1
=1.04± .04
5.6 * .2
5.2 ± .1
=1.08± .04
6.1 * .1
7.1 ± .4
=0.85± .07
1.04 ±.08
3High
calcium station:   Bl = Blend of 1,2 § 3;  B2 = Blend of 4,5 § 6;  SB = Super Bier
 PIXE target contamination, solution exhausted.
                                             244 A

-------
 1
 2
        BLENDS  OF THREE OF THE SIX SAMPLES, AND B-3, WE
        ARE CALLING IT SB HERE,  WAS A SUPER BLEND OF ALL

 3      SIX,  SO THAT REPRESENTS  COMPOSITE BEHAVIOR WHEREAS

        THE INDIVIDUAL SAMPLES  REFLECT SAMPLING VARIABILITY,

 5          FOR EACH OF THOSE,  WE MEASURED A VALUE BY

        ATOMIC  ABSORPTION WHICH  IS IN THE DENOMINATOR,   WE

        MEASURED A VALUE BY PIXE, EACH WITH A STANDARD

        DEVIATION,   WE COMPUTED  THE RATIO OF THOSE TWO

        NUMBERS WITH ITS STANDARD DEVIATION WITH A ROOT
10
        MEAN  SQUARE COMBINATION  OF ERRORS AND WE COMPUTED

        A MEAN  VALUE FOR THE ENTIRE SET OF DATA AT THIS

        PARTICULAR SAMPLING LOCATION WITH ITS STANDARD

        DEVIATION,

            FINALLY,  THE lbA SAMPLES WE DID WE COMPUTED A

        GRAND MEAN,   NOW IF EVERYTHING IS EXACTLY RIGHT,
16                                        _
        THE GRAND MEAN SHOULD BE EQUAL TO 1,0 AND ALSO,

        ANOTHER WAY OF EVALUATING THE DATA IS THAT 95
18
        PERCENT OF THE SAMPLES  SHOULD BE WITHIN TWO
19
        STANDARD DEVIATIONS OF  ONE.   THIS IS THE WAY WE
20
        ARE EVALUATING THE DATA,
21
            ON  SLIDE 10, ! HOPE  YOU CAN SEE THIS, ALTHOUGH
22
        IT IS A LITTLE DARK,  FOR CHROMIUM, OUR WORKING
23
        CONCENTRATION RANGE (AGAIN DRY WEIGHT CONCENTRATIONS)
24
        WAS ,3  TO 4 PARTS PER MILLION; THE MEAN RATIO CLEARLY
25
        IS WITHIN ONE STANDARD  DEVIATION OF UNITY, AND  SO FORTHi

-------
              Present Work

      •5N HNO3 Sediment Leachats



                              FIXE
          Dominant             AA
Element  Cone.Range    Mean RatiptS.D.
           (Dry wt)

 Cr        0.3-4ppm     1.06 ± .21

 Fe      300-2500ppra    0.99 ± .05

 Ni*       0.1-3ppm     0.97 ± .31

 Cu*       0.2-2ppm     1.07 ± .16

 3n        2 -12ppra     1.05 ± .10

 In        25-70ppm      1.02 * .04

 Pb        1 -6ppra      0.95 * .09
  *  Practically  50% or more of the
  concentrations  measured  in these metal:
 were  in  the  fraction of a ppm range.
                245A

-------
 1       THE  STANDARD  DEVIATIONS  WERE GENERALLY FAIRLY SMALL



 2       WITH THE  EXCEPTION  OF NICKEL,  AND THE REASON IT WAS



 3       SO  SMALL  IS THAT MANY OF THE NICKEL NUMBERS WERE



 4       VERY CLOSE TO DETECTION  LIMITS,  AND SO THE 30 PER-



 5       CENT RELATIVE STANDARD DEVIATION THERE REPRESENTS



 6       A LOT OF  NUMBERS THAT ARE NEAR DETECTION LIMITS



 7       FOR  ONE TECHNIQUE OR THE OTHER.



 s           SLIDE 11, PLEASE.  WE ALSO ATTEMPTED TO EVALUATE



 9       CONCENTRATION BIAS  BECAUSE A GROUP MEAN OBSCURES



10       THE  FACT  THAT YOU MIGHT  BE SYSTEMATICALLY HIGH AT



11       LOW  CONCENTRATIONS,  AND  LOW AT HIGH ONES OP. VICE



12       VERSA,  $0 THIS  IS  A PLOT OF THE PIXE/AA RATIO



13       VERSUS THE LOG OF CONCENTRATION  OVER APPROXIMATELY



14       A FACTOR  OF 50,  VARIATION IN CONCENTRATION, AS



15       MEASURED  BY ATOMIC  ABSORPTION, AND THIS IS PIXE/AA



16       RATIO,  THE VERTICAL BARS REPRESENT PLUS OR MINUS



17       ONE  STANDARD  DEVIATION IN THE RATIO.  I THINK YOU



18       CAN  SEE THAT  THE LINE WE HAVE DRAWN REPRESENTS



19       THE  DATA  WELL, AND  FURTHER THAT THERE DOES NOT



20       APPEAR TO BE  ANY DETECTABLE CONCENTRATION BIAS



21       AS  A FUNCTION OF CONCENTRATION,



22           THIS  IS FOR  COPPER CONCENTRATION, WHICH REPRESENTS



23       ONE  OF THE ELEMENTS WHERE A LOT OF THE CONCENTRATIONS



24       WERE NEAR DETECTION LIMITS,  AT LOW COPPER CONCEN-



25       TRATIONS, YOU CAN SEE BY THE VERTICAL BARS, THE

-------
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1 1 1 1 I
-0.2 0 0.2 0.4 0.6 0.8
LOG  Cu  CONC.fPpm, dry sediment)

-------
 1       STANDARD DEVIATIONS WERE QUITE LARGE.  EVEN SO
 2       THERE DOES NOT APPEAR TO BE ANY BIAS NEAR THE
 3       DETECTION LIMIT,  OF COURSE AT HIGHER CONCENTRA-
 4       TIONS THE MEASUREMENTS GOT MORE AND MORE PRECISE,
 5       SO THE NUMBERS ARE MUCH CLOSER TO THE MEAN VALUE,
 6       THIS IS THE TYPE OF PLOT THAT WE OBSERVED WITH AN
 7       ELEMENT WHERE THE CONCENTRATIONS WERE REASONABLY
 8       CLOSE TO DETECTION LIMITS,
 9           SLIDE 12 SHOWS A PLOT WHICH WAS FOR IRON,  WHICH
10       IS GENERALLY ABUNDANT IN THESE SAMPLES, AND WHERE
11       ALMOST ALL THE MEASUREMENTS WERE QUITE PRECISE.
12       AGAIN I THINK YOU CAN SEE THAT THERE is NO DETEC-
13       TABLE BIAS AS A FUNCTION OF CONCENTRATION,
14           WE DID ONE OTHER SERIES OF TESTS ON THESE
15       SAMPLES,  VIE ALSO DID A TOTAL DIGESTION,   INSTEAD
16       OF DOING THE DIGESTION THAT ! HAVE DESCRIBED HERE,
        WITH FIVE NORMAL NITRIC ACID, WE ALSO DID A TOTAL
18
        DIGESTION USING HYDROFLUORIC ACID TO DISSOLVE  THE
        SILICATE MATRIX AND IT WAS  OF INTEREST TO EXAMINE
20
        THE COMPARABILITY OF THE PIXE/AA DETERMINATIONS  ON
21                             T
        THAT TYPE OF MATRIX,  I MIGHT ADD THAT FLUORIDE
22
        CREATES A LOT OF PROBLEMS FOR US BECAUSE WHEN  FLUORIDE
        IS IRRADIATED WITH PROTON BEAMS, YOU GET SOME  VERY
24
        HIGH ENERGY PHOTONS GIVEN OFi- WHICH CAUSE PROBLEMS WITH
25
        THE DETECTOR, SO THAT REPRESENTS A DIFFICULT MATRIX
                                  247

-------
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       1.0
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    X

    a.
            1
              2.6
2.8
3.0
3.2
3.4
3.6
                 LOG Fe  CONC.(ppm, dry sediment)

-------
 1       FOR US,  FOR PIXE MEASUREMENTS,
 2

        WERE IN THAT PARTICULAR MATRIX, WHICH GENERALLY HAD
           V/E  WERE  INTERESTED IN  SEEING HOW COMPARABLE WE
3
        MUCH HIGHER CONCENTRATIONS OF THE METALS, AND ALSO
 5      IN DETERMINING WHAT FRACTION OF THE TOTAL METALS
 6      WERE AVAILABLE IN A RELATIVELY MILD TREATMENT WITH
        FIVE NORMAL NITRIC ACID,
 8          SLIDE 13 SHOWS A SUMMARY ONLY OF WHAT WE FOUND
 9      IN THIS CASE,   YOU CAN SEE, IN GENERAL, THE CONCEN-
 10      TRATION-RANGES ARE MUCH HIGHER FOR THE TOTAL DIGEST,
 11       THE RATIOS STILL ARE WITHIN ONE STANDARD DEVIATION
 12      OF ONE, BUT YOU WILL NOTICE THAT THE UNCERTAINTIES
 13      IN THOSE MEAN RATIOS ARE  MUCH LARGER, AND NICKEL
        AND COPPER VALUES ARE NOT PARTICULARLY GOOD,  THE
        LARGE UNCERTAINTY IN NICKEL VALUE IS ALMOST A DIRECT
        CONSEQUENCE OF THE AMOUNT OF IRON PRESENT IN THE
 17
        SAMPLE WHICH AT VERY HIGH LEVELS AS CONSTITUTES AN
        INTERFERENCE,   YOU WILL ALSO NOTICE THAT THERE ARE
 19
        VERY SMALL NUMBERS OF SAMPLES FOR WHICH A RATIO
 20
        COULD BE COMPUTED, THAT IS, WE EXCLUDED, IN COMPUTING
 21
        THE RATIO, THOSE NUMBERS  WHICH WERE WITHIN A FACTOR,
 22
        I  AM NOT SURE OF THE EXACT ONE, BUT  I BELIEVE IT WAS
 23
        A FACTOR OF TWO OR THREE, OF THE DETECTION LIMIT BECAUSE
 24
        OF THE VERY POOR PRECISION THAT THOSE WOULD HAVE,
25
            ON SLIDE 14, 1 HAVE A COMPARISON OF THE PERCENT

-------
 Table 8-A-5 .   PIXE/AA comparison summary for sediment total digests.


               Dominant                 PIXE/M                  No.  of
 Element        Cone.  Range         Mean Ratio + S.D.           Ratios  Computed
  Cr           10-30 ppra             1.11  ^ .39                  48a

  Fe           .3 to 3%               0.94  +_ .05                  94

  Ni           0-20-ppm               1.48  +_ .50                  18a»b

  Cu           0-5 ppm               1.49  +_ .50                  28a»c

  Zn           10-50 ppm             1.05  +. .23                  94

  Pb           6-16 ppm               1.04  ± .23                  94


a.  Unusually high background  due  to  high  fluorine  content  caused a severe
    deterioration in both  the  precision  and the detection sensitivity  as
    compared to sediment leachates (Table 8-A-l )  causing several  concen-
    trations to be below or near detection limit in these metals.

1.  Ni was  complicated in  PIXE by  severe spectral distortions  caused by
    high concentration of  fluorine.   Apparently some  low level spectral
    distortion  is still present in the analysis accepted here  for average
    PIXE/AA ratio computation.

c.  Total digest solutions received were very  dilute  (SOX)  as  compared to
    sediment leachates.  Since only a few  drops of  these solutions  are
    placed  on the PIXE film to dry, even very  low level Cu  contamination
    makes a significant contribution  to  the near detection  limit  Cu levels
    "resent in  these solutions.
                                8-A-14


                                        248A

-------
Table 8-A-5 .  PIXE/AA comparison summary for sediment total digests.
Element
Dominant
Cone . Range
PIXE/AA
Mean Ratio + S.D.
No . of
Ratios Computed
  Cr           10-30 ppra             1.11 +_ .39                  48a

  Fe           .3 to 3%              0.94 +_ .05                  94

  Ni           0-20-ppm              1.48 +_ .50                  18a»b

  Cu           o-S ppm               1.49 +_ .50                  28a»c

  Zn           10-50 ppm             1.05 +_ .23                  94

  Pb           6-16 ppm              1.04 +_ .23                  94


a.  Unusually high background due to high fluorine content caused a severe
    deterioration in both the precision and the detection sensitivity as
    compared to sediment leachates (Table 8-A-l ) causing several concen-
    trations to be below or near detection limit in these metals.

b.  Ni was complicated in PIXE by severe spectral distortions caused by
    high concentration of fluorine.  Apparently some low level spectral
    distortion is still present in the analysis accepted here for average
    PIXE/AA ratio computation.

c.  Total digest solutions received were very dilute (SOX) as compared to
    sediment leachates.   Since only a few drops of these solutions are
    placed on the PIXE film to dry, even very low level Cu contamination
    makes a significant  contribution to the near detection limit Cu levels
    present in these solutions.
                                8-A-14

                                       248B

-------
Table 8-22.   Percent  leachable of  total metal concentration Cdry weight)
            for cluster stations (A-F).
        Metal	Range of leachable/total x 100    Median %
Ba
Cd
Cr
Cu
Fe
Ni
Pb
V
Zn
<4
*
5-20
6-50
8-24
2-40
20-60
6-40
4-50
<2
*
8
25
10
16
35
15
27
     'Concentration too low.
                                         248C

-------

 1       OF THE METALS THAT WERE AVAILABLE IN THE FIVE NORMAL
 2       NITRIC ACID LEACH COMPARED TO THE TOTAL METALS AS
 3       DETERMINED BY THE SECOND DIGESTION PROCEDURE.  YOU
 4       CAN SEE IN GENERAL THEY ARE AROUND 15 PERCENT,
 5       LEAD WAS CONSIDERABLY HIGHER AT 35,  COPPER 25 PER-
 6       CENT,  AND ZINC WAS 27 PERCENT AVAILABLE,  NOW THIS
 7       IS REPRESENTATIVE OF ALL OF THE l¥l  VALUES THAT WE
 8       HAD IN THIS SET OF SAMPLES,
 9           THAT REPRESENTS A FAIRLY COMPLETE STUDY,   I THINK
10       YOU CAN SEE FROM THIS THE KINDS OF THINGS THAT WE CAN
11       DO,  I WILL JUST SHOW YOU A VERY BRIEF SET OF OTHER
12       KINDS  OF SAMPLES THAT WE ARE DOING,
13           IF I MAY HAVE SLIDE 15 PLEASE,   THIS IS REAL RAW
14       DATA,   K'E HAVE AN X, Y PLOTTER IMMEDIATELY AFTER
15       IRRADIATING THE SAMPLE WE CAN PLOT THIS DATA,  YOU
16       CANNOT SEE IT ON THE SLIDE,  BUT WE HAVE THE YIELD
17       CURVE  ON THE CHART PAPER, WHICH BASICALLY IS THE
18       RELATIVE NUMBER OF X-RAY PHOTONS PER ATOM, ALL
19       THE WAY ACROSS THE PERIODIC TABLE,   WlTH THAT
20       YEILD  CURVE AND KNOWLEDGE OF ONE ELEMENT PRESENT,
21       WE CAN DO A SEMI QUANTITATIVE ANALYSIS WITH A
22       PAIR OF DIVIDERS OFF THIS PLOT,  HOWEVER, THAT
23       IS NOT WHY I PRESENTED THIS,  I DID  THIS EXPERIMENT
24       IN THE LAB TO CONVINCE ONE OF OUR NEW LAB PEOPLE THAT
25       THEY SHOULD NOT DIP THEIR HANDS, EVEN IF THEY WERE
                                  249

-------
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            249A
                                    t
                                    r     -
                                    fc    A :.-

-------
 1       COVERED  WITH RUBBER GLOVES, IN THE ACID SOLUTION THEY WERE USING



 2       TO  WASH  LABWARE.   THIS REPRESENTS A PAIR OF RUBBER



 3       GLOVES THAT  WAS  DIPPED IN NITRIC ACID, ONE-TO-ONE,



 4       FOR A RELATIVELY SHORT PERIOD OF TIME.  EVERYBODY



 5       KNOWS THERE  IS A LOT OF ZINC IN ANY KIND OF RUBBER



 6       MATERIAL,  BUT  I  THINK YOU CAN SEE FROM THE APPEARANCE



 7       OF  THE SPECTRUM,  THERE ARE ALSO CONSIDERABLE AMOUNTS



 8       OF  TIN,  ARSENIC,  LEAD, STRONTIUM AND VARIOUS OTHER



 9       THINGS,   So  THIS IS  A CAPABILITY THAT WE HAVE OF



10       DOING A  VERY QUICK SCAN ON  A SAMPLE.  WE ALSO



11       EVALUATE MATERIALS OCCASIONALLY, GLOVE POWDER,FOR



12       EXAMPLE;  ALL LABORATORY GLOVES COME WITH POWDER IN



13       THEM,  V/E CAN  ALMOST IDENTIFY THE MANUFACTURER FROM



14       THE FINGERPRINT  CAUSED BY THE TRACE ELEMENTS PRESENT



15       AS  A POTENTIAL CONTAMINANT  IN THE LAB,  WE HAVE ALSO



16       EVALUATED PAINTS AND THAT SORT OF THING THAT WE ARE



17       GOING TO USE IN  CONSTRUCTING LAB APPARATUS,



18           THE ABILITY TO  DO A  QUICK QUALITATIVE MEASUREMENT



19       is  VERY  HELPFUL  TO US,  I MIGHT ADD ONE OTHER THING,



20       MIKE MENTIONED IT A  WHILE AGO,   PlXE IS A BLIND



21       TECHNIQUE; THAT  IS, WE DO  NOT HAVE TO HAVE PRIOR



22       KNOWLEDGE OF THE SAMPLE.   IF IT CONTAINS ANY ELEMENT



23       HIGHER THAN  ALUMINUM,IN SIGNIFICANT QUANTITIES WE



24       ARE GOING TO SEE IT, AND WE  DO NOT HAVE TO KNOW THAT



25       WE  ARE LOOKING FOR COPPER IN THE SAMPLE OR WHATEVER,
                                250

-------
 1      SO  IT  IS A VERY  GOOD  SCREENING  TOOL;  IT  NOT  ONLY
 2      GIVES  US THE NUMBER OF  ELEMENTS PRESENT,  BUT ALSO
 3      CAN GIVE US THE  QUANTITATIVE  MEASUREMENT.
 4           MAY  I HAVE  SLIDE 16  PLEASE.   THESE  ARE  SOME
 5      MEASUREMENTS WE  MADE  ON BIOTA,  CLAMS,  SCALLOPS,
 6      STARFISH, FISH AND VARIOUS BIOLOGICALS,  AND  AGAIN
 7      WE  MADE DUPLICATE MEASUREMENTS.   WE MEASURED THESE
 8      CONCENTRATIONS BY PIXE  AND ALSO BY ATOMIC  ABSORPTION,
 9      COMPUTED THE RATIO  IN EXACTLY THE SAME WAY THAT  I
10      HAVE DESCRIBED PREVIOUSLY FOR THE SEDIMENTS,  AND
11      THESE  ARE THE KINDS OF  RATIOS THAT WE  COME UP WITH,
12      AGAIN  YOU WILL NOTICE THAT THE  STANDARD  DEVIATION
13      IN  THE MEAN RATIO IS  RELATIVELY HIGH  FOR  SOMETHING
14      LIKE CHROMIUM BECAUSE OF  THE  DIFFICULTY  IN DOING
15      CHROMIUM  IN A BIOLOGICAL  SAMPLE,  BY ATOMIC ABSORPTION.
16      THESE  WERE DONE  WITH  STANDARD ADDITION,  I  MIGHT ADD,
17      THE CHROMIUM VALUES.
is           NICKEL REPRESENTS  A  SIMILAR  PROBLEM;  THE
19      CONCENTRATION OF NICKEL IN BIOLOGICALS IS  VERY LOW,
20      AND A  LOT OF THE NUMBERS  ARE  QUITE CLOSE  TO  DETECTION
21      LIMITS,
22           IF  I MIGHT  HAVE SLIDE 17 PLEASE.   THIS
23      DEMONSTRATES ANOTHER  CAPABILITY OF THE TECHNIQUE,
24      I BELIEVE.  WE CAN DO MULTIELEMENT ANALYSES  ON VERY
25      SMALL  SAMPLE SIZES,   THIS HAPPENS TO  BE  BLOOD PLASMA,
                                  .251

-------
                   PIXE-AA Comparison Summary - Biota Total Digests


                  Dominant               PIXE/AA               No.  of Ratios
Element         Cone.  Range          Mean Ratio ±  S.  D.         Computed	

  Cr            0-5 ppm                1.09 ± .46                  16
  Fe            100-3000 ppm           1.01 ± .22                 157

  Ni            0-5 ppm                1.03 ± .56                  80

  Cu            10-100 ppm             1.09 ± .16                 175

  Zn            50-1000 ppm            0.96 ± .11                 177

  Cd            0-10 ppm               1.02 ± .17                  62

  Pb            0.5-13 ppm             1.22 ± .35                  86t
               tStandard addition analyses were performed for all samples
                for Cr,  Fe and Pb.  Severe suppression (20-50% recovery in
                standard addition analyses) of flameless AA absorbance
                readings for Pb was observed in a large number of samples.
                Because  of the severity of matrix suppression of AA read-
                ings,  it is suspected that standard addition corrections
                did not  completely compensate for the suppression, thus
                causing  the average PIXE/AA ratio to be somewhat greater
                than 1.0 for Pb.  Some of the samples also had a very
                small mass (50-100 mg dry weight digested to yield 25 ml
                final volume) which combined with their very low Pb con-
                centration in the dry sample made the final solutions ex-
                tremely  dilute in Pb and, therefore, more sensitive to
                even low level Pb contamination.  (Pb is a common contaminant).
                                          251A

-------
W
CONC. ARE  IN  UG/G UNLESS NOTED ABOVE  VALUE

     (CA)    S      CL    CR    MN    ff£l    NI
                                                            HUMAN BLOOD PLASMA

                                                              1NJ          AS
1020
10
930
10
1010
10
1010
10
950
IP
1000
10
90.
2.
84.
2.
89.
2.
97.
2.
95.
2.
90.
2.
1280
20
1140
20
1220
20
1310
20
1230
20
1200
20
4220
60
3950
50
4140
60
4200
60
4110
50
4240
50
ND
.2
ND
.2
ND
.2
ND
.2

ND
• 2
ND
.1
ND
.2
ND
.1
• 3
.1

ND
.1
2.7
.1
1.98
.10
1.4
• 1
1.3
.1
1.4
.1
1.8
• 1
ND
• 10
ND
• 08
ND
.10
ND
.10

ND
.09
.86
.00
.81
.07
.89
.07
.86
.08
.87
.07
.85
.05
• 05
1.21
.04
1.2fl
.05
1.32
.05
1.36
.05
1.25
• 04
3.59
.07
3.47
.06
3.54
.07
3.67
.07
3.54
.06
3.46
.06
ND
.03
ND
.02
ND
.02
ND
.02

ND
.02
• 10
.02
.09
.02
.11
.02
.14
• 02
.13
.02
• 12
• 02
1.13
• 04
1.09
.03
1*19
• 04
1.19
1.16
.03
1.T6
.03
.06
.01
.05
• 01
• 06
.01
.00
.01
.06
.01
.04
• 01
    1060    90*   1160  4100   ND     ND    1.6   ND     .80   1.20   3.55   ND     .09   1.18   .04
      10     2*     20    50     .2     .1    •!   .08    .06    .04    .06   «02    .02    .03   .01
    1070    08.   1210  4070   NO     ND   1.82   ND
      10     1.     20    50.     .2     .2   .08   .07
                                                  »84  1.22   3.53    ND    .10  1.23   .050
                                                  .06   .04    .06    »02   «02    .03   .QIC

-------
 1      AND WE CAN  EASILY DETECT,  WITH  A FAIRLY ROUTINE



 2      MEASUREMENT, ABOUT  10  OR  12  ELEMENTS  IN THIS PLASMA



 3      INCLUDING SELENIUM,  RUBIDIUM, STRONTIUM WHICH ARE



 4      LESS COMMONLY DETERMINED  IN  BLOOD PLASMA,  BUT



 5      NEVERTHELESS RESULT  FROM  THE SINGLE MEASUREMENT,



 6      I MIGHT ADD, THIS SET  OF  DATA IS DONE ON 100 MICROLITERS



 7      OF BLOOD PLASMA, SO  WE DO NOT NEED A  LARGE VOLUME.   WE



 8      CAN PUSH THAT FURTHER;  I  AM  QUITE SURE WE  COULD DO



 9      A REASONABLE ANALYSIS  ON  AS  LITTLE AS 10 OR 20



10      MICROLITERS.  WE PREFER TO USE  LARGER AMOUNTS BECAUSE



11      IT IS MORE  REPRESENTATIVE AND MAKES US LESS PRONE TO



12      PARTICULATE CONTAMINATION, WHICH IS ONE OF  THE PROBLEMS



13      WITH A TECHNIQUE LIKE  PIXE.



14           THE BOTTOM THREE  REPRESENT THREE SEPARATE



15      100-MICROLITER PORTIONS OF THE  SAME PLASMA SAMPLE,



16      EACH RUN INDEPENDENTLY THROUGH  THE PIXE ANALYSIS,



17      EACH DOPED  IN THE LAB  INDEPENDENTLY AND RUN THROUGH



18      THE ANALYSIS,  I THINK YOU CAN  SEE FROM THE



19      REPRODUCIBILITY HERE THAT WE CAN,  IN  FACT, IN A



20      RATHER DIFFICULT MATRIX  GET  EXCELLENT RESULTS,  BY



21       THE  WAY,  THERE WAS  NO  DIGESTION PERFORMED ON THESE



22       SAMPLES  EITHER,  SO  ALL THE PROTEINS  AND LIPIDS AND



23       EVERYTHING ELSE  WERE STILL  IN THE BLOOD PLASMA SAMPLE,



24           TWO FINAL SLIDES.  THESE ARE SOME SAMPLES WE



25      ARE DOING FOR AN AGENCY THAT IS INTERESTED IN ANIMAL
                               252

-------
1       EXPERIMENTS, AND ONE OF THE VERY  IMPORTANT THINGS
2       IN A NUTRITIONAL SENSE IS TO KNOW COMPLETELY THE
3      TRACE ELEMENTS THAT ARE IN THE DIET,  THERE  IS A NEED
4      TO MONITOR THINGS WHICH ARE ADDED TO THE  FEED SUCH
5      AS SELENIUM, MOLYBDENUM AND SO FORTHj THOSE ARE NOT
6      TOXIC ELEMENTS BUT ADDED AS A NECESSARY DIETARY
7      INGREDIENT,  ALSO, OF COURSE, IT  IS OF  INTEREST
8      TO GET  SOME  INFORMATION ON ELEMENTS THAT  MAY NOT BE
9      ADDED BUT MAY BE FORTUITOUSLY PRESENT AND REPRESENT
10      A POSSIBLE  INTERFERENCE WITH THE  MEASUREMENTS THEY
n      ARE  TRYING  TO MAKE.
12           I HAVE  OMITTED  FROM SLIDE 18  ALL THE  ELEMENTS
13      WHICH WERE  NOT DETECTED  IN THESE  PARTICULAR  SAMPLES,
14      THESE TWO ARE TWO  COMPLETELY  INDEPENDENT  DETERMINA-
15      TIONS ON AN ACID DIGESTED  RAT DIET,  THE  BOTTOM  SET
16      OF DATA IS  TWO ADDITIONAL  MEASUREMENTS  ON A  DIFFERENT
17      RAT  DIET AND THE BOTTOM LINE  IS  THE  MEAN  AND STANDARD
18      DEVIATION OF THOSE TWO  SEPARATE  DETERMINATIONS,
19           ON  SLIDE 19  I  HAVE  SOME  ADDITIONAL  ELEMENTS,
20       I  THINK YOU CAN  SEE HERE,  I  POINT OUT,  FOR  EXAMPLE,
21      THE  SELENIUM VALUES,   THESE  ARE  ALSO PARTS  PER
22       MILLION DRY WEIGHT IN SOMETHING  THAT CONTAINS A LOT
23       OF ORGANIC  MATERIAL BEFORE THE DIGESTION,  YOU CAN
24       SEE  THAT THE TWO REPLICATE PIXE TARGETS ARE IN VERY
25
                                 253

-------
            PIXE Analyses  of Purified Rat  Diets






 Average Tables - Concentrations  are in  UG/G Unless  Noted











5     K      CA     TI   V    CR     MN     FE     CO    NI     CU     ZN
RD
1892

Mean
(s.d.)
N5
Ul
U>
RD
1894

Mean
(s.d.)
440
30
530
90
480
70
p
530
90
520
90
530
70
500
20
610
30
550
70
£
590
30
5SO
30
590
20
1290
50
1570
50
1400
200
1C
1580
50
1490
40
1530
60
920
40
1150
40
1000
200
CA
1030
30
1010
30
1020
20
ND
.7
.8
.3
.4
.6
II
ND
.6
ND
.4
,0
.4
.8
.2
.9
.3
,9
.2
V
.9
.4
ND
.3
.7
.3
.7
.3
1.2
.5
1.0
.3
CR
ND
.4
1.2
.4
.7
.6
32.
1.
38.
1.
35.
4.
MN
36.
1.
34.4
1.0
35.0
.8
14.0
.7
17.2
.7
16.
2.
FE
11.5
.6
10.9
.5
11.2
.5
.4
.1
.7
.1
.5
.2
CO
ND
.1
ND
.07
.00
.07
ND
.06
ND
.05
.05
,04
NI
ND
.06
ND
.05
.03
.04
1.6
.1
1.72
.10
1.66
.08
CU
1.6
.1
1.6
.1
1.60
.08
11.7
.3
13.5
.4
13.
1.
ZN
21.2
.6
20.9
.5
21.0
.4

-------
CO
W
                                     PIXE Analyses of Purified Rat  Diets


                          Average Tables - Concentrations  are in UG/G  Unless Noted
                             AS    SE    RB    SR    ZR    MO     CD    TE    PT     PB
RD
1892

Mean
(s.d.)

RD
1894

Mean
(s.d.)
.07
.01
ND
.02
.05
.03
AS
ND
.02
ND
.01
.00
.01
.80
.03
.85
.03
.82
.03
§§.
.64
.03
.69
.03
.66
.04
ND
.01
.08
.02
.05
.04
RB
.06
.02
.07
.02
.07
.01
.93
.04
1.01
,04
.97
.06
SR
.92
.04
.99
.04
.96
.05
.11
.03
.18
.03
.15
.05
ZR
.17
.02
.15
.02
.16
.02
.85
.05
.96
.05
.91
.08
MO
1.46
.07
1.49
.06
1.47
.05
ND
.07
.17
.08
.1
.1
cp_
.21
.10
.22
.08
.22
.06
1.1
.4
.8
.4
.9
.3
TE
.9
.4
1.3
.3
1.1
.2
ND
.07.
ND
.08
.02
.05
PT
ND
.07
ND
.05
.03
.05
ND
.03
.13
.03
.09
.05
PB
.25
.04
.29
.03
.27
.03

-------
 1      GOOD AGREEMENT  AND  THAT  WE  CAN  EASILY DISTINGUISH
 2      DIFFERENT DIETARY LEVELS OF THE SELENIUM FROM THE
 3      SAMPLE; OTHER THINGS  THAT ARE FORTUITOUSLY PRESENT,
 4      RUBIDIUM, ZIRCONIUM,  QUITE  A BIT,  AND SOMETHING  OF
 5      CONSIDERABLE  INTEREST TO ME IS  TELLURIUM,   '«/E HAVE
 6      BEEN CALIBRATED FOR TELLURIUM FOR  A  LONG PERIOD  OF
 7      TIME, BUT I HAD NOT SEEN IT IN  NATURAL SAMPLES UNTIL
 8      RECENTLY,  $0 YOU CAN SEE THAT  IT  IS  PRESENT  IN  DIETS, WE
 9      HAVE SEEN IT  IN TISSUE SAMPLES.  THAT ELEMENT IS NOT
10      ON THE CURRENT  PRIORITY  POLLUTANT  LIST AND IT IS NOT
11      MY POSITION TO  MAKE RECOMMENDATIONS,  BUT WE CAN
12      MEASURE THE ELEMENT IN A VARIETY OF  SAMPLES,   HE HAVE
13      ALSO SEEN IT  IN SOME  INORGANICS AND  SO FORTH,
14           THAT is THE LAST OF THE SLIDES,   LET ME  JUST
15      CLOSE BY POINTING OUT TO YOU A  FEW AREAS WHERE I
16      THINK THE CAPABILITIES OF PIXE  REPRESENT SOME
17      COMPLEMENTARY MEASUREMENTS  THAT WILL ADD TO THE  DATA
18      AVAILABLE BY A  TECHNIQUE WHICH  REQUIRES A SOLUBLE
19      SAMPLE AS A PRACTICAL MATTER,   WE  HAVE THE CAPABILITY
20      OF ANALYZING THINGS LIKE SUSPENDED PARTICULATE MATTER,
21      I THINK AN  INTERESTING QUESTION CAME UP YESTERDAY
22      WHEN WE WERE TALKING  ABOUT  THE  RECOVERY OF THE ORGANIC
23      PRIORITY POLLUTANTS FROM A  SAMPLE  WHICH CONTAINS
24      PARTICULATES, AND THE QUESTION  WAS RAISED AS  TO  WHETHER
25      THERE MIGHT BE  METALS ON THOSE  PARTICULATES WHICH WOULD
                                 254

-------
 1      COMPLEX THE  ORGANICS  AND  CAUSE  A TRANSFER,   WE HAVE
 2      DONE  PARTICULATES  ISOLATED  FROM BOTH WATER  AND AIR
 3      SAMPLES.  WE ARE SET  UP TO  ANALYZE SAMPLES  ON
 4       NUCLEOPORE,  MILLIPORE, BOTH  47 MILLIMETERS AND 37 MILL I METE
 5      SAMPLES,  ALL THAT IS NECESSARY FOR US  TO CONDUCT
 6      THIS  ANALYSIS IS TO MOUNT THE DRIED FILTER, OBTAIN
 7      A SAMPLE, OF COURSE,  TO MOUNT THE DRY FILTER
 8       IN A  PLASTIC HOLDER THAT  WE HAVE DESIGNED FOR THE
 9      PURPOSE, ASSEMBLE  IT  INTO THE TRAY AS WE  DO IT,
10       IN OTHER WORDS, NO DIGESTION  IS REQUIRED  IN ORDER TO
11      DO THAT ANALYSIS,
12            NOW,  IF ANY OF YOU HAVE  DONE SUSPENDED
13      PARTICULATE  MATTER BY MORE  CONVENTIONAL PROCEDURES,
14      THAT  IS, DIGESTING  A ONE-MILLIGRAM SAMPLE, OR SOMETHING
15      OF THAT ORDER,  AND MAKING IT  UP TO ENOUGH VOLUME  TO DO
16      A MULTIELEMENTAL ATOMIC ABSORPTION ANALYSIS, YOU
17      RECOGNIZE ALL OF THE  PROBLEMS YOU HAVE  WITH
18      CONTAMINATION AND  DETECTION LIMITS,   $0 WE  ARE ABLE TO
19      DO AIR  PARTICULATES AND PARTICULATES IN WATER OR  SOME
20      SORT  OF A SOLUTION ENVIRONMENT,  WE CAN ANALYZE
21      TISSUE  SLICES,   IT IS NOT NECESSARY TO  DO A DIGESTION,
22       IF YOU  HAVE  A THIN SAMPLE,  WHICH COULD  BE A BIOPSY
23      OR A  THIN FILM, POLYMER FILMS,   OF COURSE THAT IS
24      ONE OF  OUR REAL PROBLEMS  IS TO  KEEP OUR POLYMER FILMS
25      CLEAN ENOUGH SO THAT  WE DO  NOT  HAVE ANY SIGNIFICANT

-------
 1      CONTAMINATION., BUT WE ARE  SET  UP  TO  ROUTINELY MEASURE
 2      THOSE,  SLAGS, WE ARE ABLE TO  DO  POWDERED SLAG SAMPLES
 3      AND WE HAVE ALSO DONE COMPARISONS WITH  THE DIGESTED
 4      SLAG SAMPLE,
 5           ONE FINAL THING THAT  M.IKE MENTIONED  BEFORE THAT
 6      I WOULD LIKE TO REITERATE,   IT IS QUITE OBVIOUS THAT
 7      SOME SAMPLES, AND I CANNOT CLAIM  TO  HAVE  SEEN A
 8      REPRESENTATIVE SET, DO  LEAVE A SUBSTANTIAL RESIDUE
 9      AFTER THE CONVENTIONAL  EPA PROCEDURE,   IN THE PAST,
10      I THINK IN MOST CASES THIS RESIDUE HAS  BEEN
11      FILTERED OUT AND DISCARDED, BUT WE ARE  LOSING AN
12      AWFUL LOT OF INFORMATION AND I DO NOT WANT TO POINT
13      OUT ANY SPECIFICS, BUT  THERE ARE  A LOT  OF ELEMENTS  IN
14      OUR EXPERIENCE WITH A VARIETY  OF  DIGESTIONS THAT
15      TYPICALLY COME UP IN THIS  PRECIPITATE SUCH AS
16      TITANIUM, NIOBIUM, STRONTIUM,  POTASSIUM,  RUBIDIUM,
17      AND THERE CAN EASILY BE SOME CARRY-OVER OF
18      SOME OF THE PRIORITY POLLUTANTS AS WELL.
19           So WE ARE ABLE, IN THE  COURSE OF THE DIGESTION,
20      IF A PRECIPITATE  IS FORMED,  AS LONG  AS  THE PARTICLE
21      SIZE IS SUFFICIENTLY SMALL,  WE CAN GET  A  QUANTITATIVE
22      MEASURE OF THE ELEMENTAL CONSTITUTENTS  IN THAT
"      PRECIPITATE; IN THE EVENT  THAT THE PARTICLE SIZE is
24      TOO LARGE, WE CAN AT LEAST IDENTIFY  ELEMENTS PRESENT
25      EASILY WITHOUT WORRYING ABOUT  THE ACCURACY OF AN X-RAY

-------
1      ATTENUATION  CORRECTION,
2           THANK YOU  VERY MUCH,
3                                MR, CARTER:   IF ANYONE  WOULD
4      LIKE TO ASK  ANY QUESTIONS AT THIS POINT, WE WOULD
5      ATTEMPT TO ANSWER THEM,
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
                                 257

-------
258

-------
 i                       QUESTION AND ANSWER
 2                             SESSION
 3
 4                                MR,  DAVIS:   I  HAVE SEVERAL;
 5      ABE  DAVIS,   HOOKER CHEMICAL.   WOULD YOU COMMENT ON
 6      THE  MATRIX  AND SENSITIVITY,  MATRIX EFFECTS, ABSORPTION
 7      ENHANCEMENT AND SENSITIVITY  OF THIS  METHOD  AS
 8      OPPOSED,  SAY,  TO X-RAY FLUORESCENCE,  BOTH ENERGY AND
 9      WAVELENGTH  DISPERSIVEj IS IT COMPLEMENTARY  OR
10      DOES IT  COVER  A WIDER RANGE?
11                                DR,  GRANT:   I  WOULD SAY THAT
12      THE  INTERFERENCES IN OUR TECHNIQUE,  LET ME  PREFACE
13      MY REMARKS  BY  SAYING I DO NOT DO X-RAY  CLUORESCENCE
14      SO I AM  NOT INTIMATELY AWARE OF THE SPECIFIC PROBLEMS
15      THERE, BUT  I WOULD VENTURE TO SAY THAT  THE  MAJOR
16       INTERFERENCES  WITH THE TECHNIQUE CONSIST OF SPECTRAL
17      OVERLAPS,   AS  I SAID, EACH ELEMENT IS CHARACTERIZED
18      BY A MULTIPLET  OF LINES, AND IN GENERAL,  IN THE
19      FIRST ROW  TRANSITION ELEMENTS, THE K'ALPHA LINE
20      OF THE NEXT ELEMENT IN THE PERIODIC TABLE OVERLAPS
21      THE  K-BETA  LINE OF THE PRECEDING ONE, SO THAT  IS THE
22      SOURCE OF THE  INTERFERENCE THAT I MENTIONED, THAT
23      LARGE AMOUNTS  OF IRON INTERFERE WITH NICKEL BECAUSE
24       IT IS AN ADJACENT ELEMENT.  So WE HAVE  MUCH THE SAME
25       INTERFERENCES  IN THAT CASE THAT X-RAY FLUORESCENCE HAS,
                                 259

-------
 1           THE CHIEF DIFFERENCE  BETWEEN,  I  THINK,THE



 2      CONVENTIONAL X-RAY  FLUORESCENCE  AND THE PIXE PROCEDURE



 3      IS  IN THE  EFFICIENCY  WITH  WHICH  THE X-RAYS ARE



 4      GENERATED, AND  IN THE BACKGROUND RADIATION AT HIGHER



 5      ENERGY  LEVELS, AND  THIS  ENABLES  US  TO GET A BETTER



 6      SIGNAL-TO-NOISE  RATIO FOR THE HEAVY  ELEMENTS LIKE



 7      INDIUM  AND CADMIUM, TIN,  IN THAT RANGE OF THE SPECTRUM,



 8      SAY  FROM THE MIDPOINT OUT,  SO WE DO GET IMPROVED



 9      SENSITIVITIES BECAUSE OF THAT,   OUR COMPUTER PROGRAM,



10      WE  HAVE A  VERY SLOW COMPUTER AT  THE MOMENT,  BUT IT



11      TAKES BETWEEN AN HOUR AND  TWO HOURS TO COMPUTE THE



12      RESULTS OF THIS SPECTRUM,  SO WE  ARE DOING A LOT OF



13      THINGS, WE DO CORRECT AUTOMATICALLY FOUR INTERFERENCES,



14      THAT IS, OVERLAPPING PEAKS,  AND THAT, UNCERTAINLY, I



15      NEGLECTED  TO MENTION  IT  WHEN I MENTIONED HOW WE GET



16      A STANDARD DEVIATION, IS  ALSO FOLDED INTO THE STANDARD



17      DEVIATION.



18           I  GUESS THE BEST MEASURE  I  WOULD SAY WITH HOW



19      WELL WE ARE ABLE TO DECONVULUTE  SPECTRUM IS,,,SEVERAL



20      OF  THOSE TABLES  I SHOWED YOU INCLUDED DUPLICATE TARGETS,



21      TWO TARGETS MADE FROM THE  SAME SOLUTION,  THERE IS NO



22      QUESTION ABOUT  HOW  WELL  YOU PREPARED YOUR SAMPLES  OR



23      ANY OF  THAT;  IT  IS  SIMPLY  MEASURING THE REPLICATION



24      IN  THE  PIXE MEASUREMENT  ITSELF,  AND I THINK YOU WILL



25      NOTICE, I  HOPE YOU  WILL  RECALL,  THAT IN GENERAL THE

-------
1      REPLICATION BETWEEN TWO TARGETS WAS  AS  GOOD  AS  THE
2      ESTIMATED STATISTICAL  UNCERTAINTY  ON ANY  INDIVIDUAL
3      TARGET, WHICH MEANS THAT  OUR  ERROR ESTIMATES ARE  QUITE
4      REASONABLE.
5                                FIR,  DAVIS:   WHAT I  WAS
6      CONCERNED WITH  IS, OF  COURSE  YOU HAVE THE SPECTRAL
7      OVERLAP, K-ALPHA, K-BETA  TYPE OF THING; THAT HAS  GOT
8      TO BE WITH THE  EMISSION SPECTRA THAT YOU  ARE LOOKING
9      AT, BUT WHAT  I  AM CONCERNED ABOUT, YOU  BROUGHT  UP
10      THE IRON-NICKEL,  DOES A  PRESENCE  OF A  LARGE AMOUNT
11      OF  IRON REDUCE  THE NICKEL BECAUSE  THE IRON ABSORBS,
12      OR DOES YOUR  THIN FILM TECHNIQUE REDUCE THAT MATRIX
13      EFFECT, ABSORPTION  IN  THIS CASE, OR  ENHANCEMENT IN
14      OTHER CASES,  THE  FACT  THAT IRONS ENHANCE,  DO YOU  HAVE
15      TO RESORT TO  SOMETHING LIKE COLBY'S  MAGIC PROGRAM,
16      THAT  IS WHAT  I  AM CONCERNED ABOUT,
17                                DR,  GRANT:   I  CANNOT COMMENT
18      ON THE DETAILS  BECAUSE I  DID  NOT WRITE  THE PROGRAM
19      THAT  COMPUTES THE CORRECTION  AND THAT PERSON IS NOT
20      HERE.  HOWEVER, I COULD RESPOND TO THAT IN MORE
21      DETAIL  IF YOU ARE  INTERESTED, As  FAR AS  THE QUESTION
22      OF WHETHER A  PRESENCE  OF  A LARGE AMOUNT OF IRON WOULD
23      INTERFERE WITH A LIGHTER ELEMENT BY X-RAY  ATTENUATION,
24      YES,  THAT  IS  A  PROBLEM IF THE THICKNESS OF THE S'AMPLE
25      ON THE TARGET,  WHETHER IT ARISES  FROM A POWDERED SAMPLE
                                 _2fil

-------
 1       OR  A  SPOTTED  SOLUBLE  SAMPLE,  IF  THE  THICKNESS  IS
 2       SUFFICIENTLY  LARGE, THERE  WILL CERTAINLY BE X~RAY
 3       ATTENUATION,  WE  HAVE THE  PROGRAM, WE  DO A TWO-PASS
 4       CALCULATION,  THE FIRST  PASS  DOES  NOT  ASSUME ANY
 5       ABSORPTION,   THEN THE THICKNESS  OF ANY ELEMENT ON
 6       THAT  TARGET IS COMPUTED  FROM  THE FIRST PASS CALCULATION,
 7       SO  FOR  EXAMPLE,  IF THERE  IS A LOT  OF IRON ON THE TARGET
 8       WE  COMPUTE THE NUMBER OF NANOGRAMS PER SQUARE
 9       CENTIMETER OF IRON ON OUR  TARGET,  AND  FROM THAT THE
10       CORRECTION IS ESTIMATED AND A SECOND PASS IS DONE
11       WHICH DOES THE CALCULATION FOR ATTENTUATION FOR ALL
12       OF  THE  LIGHTER ELEMENTS, AND  ALSO  SELF-ATTENTUATION
13       FOR IRON,
14            WE HAVE  A HARD COPY PRINTOUT  OF BOTH OF THOSE
15       SO  THAT WE CAN GO BACK AND LOOK  AT THEM AND SEE
16       WHETHER THERE WAS A SIGNIFICANT  CORRECTION COMPUTED,
17       AND I MIGHT ADD THAT  EVEN  THOUGH ALL OF OUR
18       DECONVOLUTION IS  UNDER COMPUTER  CONTROL,  THE FINAL
19       STEP  IN EVERY ONE OF  OUR PROCEDURES  IS TO EXAMINE
20       MANUALLY THE  FIT,  THE AGREEMENT  AND  FIT BETWEEN THE
21       COMPUTED CURVE AND THE DATA MINUS  BACKGROUND CURVE
22       AND IF  THEY DON'T OVERLAP  SATISFACTORILY, A NEW
23       CALCULATION IS DONE.   THERE ARE  SOME ADJUSTMENTS THAT
24       CAN BE  MADE IN THE CALCULATION,  So  YES, WE DO HAVE
25       A THICKNESS CORRECTION, BUT OUR  GENERAL APPROACH TO

-------
 1      THAT  IS  IF WE  HAD  A  SAMPLE  WITH A LARGE AMOUNT OF
 2      IRON  IN  IT AND WE  RAN  A  TARGET AND FOUND THAT  SIGNIFICANT
 3      CORRECTIONS WERE TO  BE MADE,  WE WOULD  IN GENERAL TRY
 4      TO GO BACK AND DILUTE  THE SAMPLE SO THAT THE AVERAGE
 5      CONCENTRATION  OF  IRON  IN THE  SAMPLE WERE LOWER AND  REDO
 6      THE ENTIRE CALCULATION,
 i                               MR,  DAVIS:  ONE LAST  QUESTION,
 8      HAVE  YOU  TRIED USING THE MILLEPORE FILTERS  AS  A PLACE
 9      TO YOUR  SPECIAL PLASTIC, AND  WOULD YOU  COMMENT ON THE
10      SAMPLE PREP BECAUSE  I  THINK YOUR PROBLEMS ARE  VERY
11      SIMILAR  TO THOSE THAT  X-RAY FLUORSCENCE MUST
12      EXPERIENCE.
13                               DR,  GRANT:  I  AM NOT  SURE
14      WHAT  YOU  MEAN  BY THE SAMPLE PREP RATHER THAN THE
15      MILLEPORE.,,
16                               MR,  DAVIS:  SAMPLE PREP,
17      HOW DO YOU GET IT  ONTO THE  FILM, HOW DO YOU KEEP  THE
18      THICKNESS UNIFORM, ET  CETERA,   I REALIZE YOU SPIN
19      AND THIS  WILL  AVERAGE  OUT THESE, SHALL  WE SAY
20      NONUNIFORMITY  OF THE THICKNESS,
21                               DR,  GRANT:  YES,
22                               MR,  DAVIS:  I  THINK THE  SAMPLE
23      PREP  IS  QUITE  CRITICAL,  AND CAN YOU GET AWAY WITH THE
24      COMMERCIAL FILTER  SUCH AS MILLEPORE?
25                               DR,  GRANT:  IN MOST OF THE

-------
 1      PIXE DETERMINATIONS  ACROSS  137  MILLIMETER  FILTER TO
 2      GET THE DISTRIBUTION ACROSS THE DIAMETER.  AND  FROM
 3      THAT YOU  CAN  INTEGRATE  THE  AREA UNDER  THE  CURVE  AND
 4      OBTAIN A  QUANTITATIVE MEASURE ON THE ENTIRE  SAMPLE.
 5      THAT OF COURSE  REQUIRES SEVEN PIXE  MEASUREMENTS  INSTEAD
 6      OF ONE. BUT EVEN  IN  A NONUNIFORM DISTRIBUTION  WE CAN
 7      STILL GET A QUANTITATIVE ANSWER ON  THE THING,
 8            I WOULD  SAY, NOT HAVING A TREMENDOUS AMOUNT  OF
 9      EXPERIENCE WITH THE  SAMPLING FILTERS,  I WOULD  SAY
 10      THERE ARE SOME  REAL  PROBLEMS WITH GETTING  UNIFORM
 11      FILTERS ON THAT TECHNIQUE.   OF  COURSE,IF YOU DO  A
 12      DIGESTION OF  THAT FILTER, THAT  KIND OF ELIMINATES
 13      THE PROBLEM,  BUT  IT  ADDS IN ALL OF  THE COMPLICATIONS
 14      WITH BLANK CONTAMINATION, LOSS  OF SAMPLES, THE
 15      COMPLETENESS  OF THE  DIGESTION AND THAT SORT  OF THING,
 16                                MR, BLUM:  SAUL BLUM, EXXON
 17      RESEARCH,   I  DON'T HAVE A QUESTION, I  HAVE A COMMENT,
 18      ONE OF THE SLIDES, I BELIEVE IT WAS ON LEACH EGG,
 19      SHOWED QUADRUPLICATE RESULTS FROM WHICH AVERAGE  AND
 20      STANDARD  DEVIATIONS  WERE COMPUTED,   I  RAN  THROUGH THE
 21      CALCULATION BECAUSE  IT  LOOKED A LITTLE OPTIMISTIC,
 22      IT LOOKED AS  IF A POPULATION STANDARD  DEVIATION
 23      WAS COMPUTED,   YOU MIGHT WANT TO GO BACK AND RECHECK
 24      THOSE; YOU SHOULD BE USING  A SAMPLE STANDARD DEVIATION
25      WHICH WOULD MAKE  THE NUMBERS SOMEWHAT  HIGHER,
                                 265

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                            DR,  GRANT:   THANK YOU, I WILL
   HAVE TO GO BACK AND CHECK THAT,
                            FIR, C.A.RTER:  IF THERE ARE NO
   MORE QUESTIONS, THERE IS SOME  COFFEE OUTSIDE, SO YOU CAN
   TAKE A BREAK,
        THE NEXT  PRESENTATION WAS SCHEDULED FOR 10 AND
   IT IS ABOUT FIVE UNTIL 10 RIGHT NOW,  MAYBE WE CAN
   SHOOT FOR ABOUT A 10:20 RECONVOCATION HERE,
(WHEREUPON, A BREAK WAS TAKEN,)
                            MR,  TELLIARD:   WE HAVE UP
   HERE WITH US TODAY BOB FlEDZ FROM THE OFPl'CE OF RESEARCH,
   BOB IS CHAIRMAN OF THE 304-H  COMMITTEE, WHICH IS
   CHARGED WITH PUTTING OUT 'METHODS'  FOR  THE MEASUREMENT
   OF 'POLLUTANTS,'   You HAVE SEEN THE FIRST PART OF
   TWO, WHICH WERE RECENTLY PROPOSED,  BASICALLY
   COVERING THE ORGANICS, ICAP PROCEDURE.   THERE IS A
   SECOND PACKAGE WHICH WILL CONTAIN BIOMONITORING, SOME
   OF THE METHODOLOGY USED IN THE ORGANIC  CHEMICALS GROUP,
   THE MICROEXTRACTION TECHNIQUE, THE METHODS FOR ASBESTOS,
   AND A DEFINITION FOR DETECTION LIMIT, AND AN UPDATE
   OF ALL THE TABLE REFERENCES FOR METALS  AND RESIDUAL
   CHLORINE AND WHATEVER ELSE,
        WE CAN BE HAPPY TO ANSWER ANY OF YOUR QUESTIONS,
   AND THE ONLY THING WE CANNOT  DO IS GRANT YOU AN
   EXTENSION ON THE COMMENT PERIOD,
                            266

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 i                                VOICE  FROM THE AUDIENCE:   WHEN
 2       IS THE  SECOND  PACKAGE  GOING  TO  BE  AVAILABLE?
 3                                MR,  MEDZ:   THE COMMITTEE  WILL
 4       BE MEETING  IN  THE  MIDDLE  OF  FEBRUARY TO CONSIDER THE
 5       SECOND  PACKAGE AND GIVE  ITS  FINAL  APPROVAL AS  TO WHAT
 6       WILL BE IN  THE SECOND  PACKAGE,   YOU HAVE HAD AN
 7       APPROXIMATION  OF WHAT  IT  WILL CONTAIN,  BUT THE
 s       COMMITTEE WILL DETERMINE  ITS FINAL NATURE,   WE WOULD
 9       BE CONVENING  IN MID-FEBRUARY ON THAT, WHICH MEANS
10       IT WILL PROBABLY BE PREPARED SOMETIME IN MARCH,
11                                MR,  TELLIARD:   ANY QUESTIONS?
12                                MR,  HAMLIN:   PHIL HAMLIN,
13       ITT RAYONIER,   I HAD SOME OTHER QUESTIONS, OTHER THAN
14       ON THE  304  METHODS, BUT  I WOULD LIKE TO ASK SOME
15       QUESTIONS ON  THOSE, TOO,
IB           WHAT is  GOING TO  BE  THE PURPOSE OF THE CARBONACEOUS
17       BOD METHOD?
is                                MR,  MEDZ:   THE CARBONACEOUS
19       BOD METHOD  IS  A COMPLETELY NEW  PARAMETER,   SOME OF
20       THE STATES  WANT TO INCLUDE CARBONACEOUS BOD IN SOME
21       OF THE  THINGS  THEY ARE DOING,   THEY WANT AN IMPROVED
22       METHOD  BY WHICH THEY COULD MAKE MEASUREMENTS OF
23       CARBONACEOUS BOD,   THE QUESTION HAS COME UP, IS
24       CARBONACEOUS BOD GOING TO BE AN APPROVED OPTION TO
25       THE CONVENTIONAL FIVE-DAY BOD,   No,  THAT IS NOT THE

-------
 1       INTENTION  OF  THE  PROPOSAL.   IT IS A COMPLETELY NEW
 2       PARAMETER,  As  OF THIS  TIME,  NO LIMITATIONS HAVE BEEN
 3       WRITTEN  ON CARBONACEOUS BOD,   SOME OF THE PERMITS
 4       PEOPLE USING  THE  BEST ENGINEERING JUDGMENT MIGHT
 5       CHOOSE TO  WANT  TO USE  IT ALSO AS A MEASURE OF SOME OF
 6       THE  PERMITTING  CONDITIONS,  BUT UP UNTIL NOW,
 7       CARBONACEOUS  BOD  HAS NOT BEEN USED,
 8                                MR,  HAMLIN:   Do YOU
 9       ANTICIPATE A  SCREENING  OR VERIFICATION PHASE AS TO
 10       REASONABLE LEVELS OF CONTROL  :FOR CARBONACEOUS BOD
 11       IF  IT  IS PROPOSED TO PUT THAT OUT ASA PERMIT LIMITATION?
 12                                FIR,  MEDZ:  As FAR AS THE
 13       SCREENING  LEVEL TO BE PROPOSED ASSOCIATED WITH THE
 14       CARBONACEOUS  BOD, THAT  HAS  NOT BEEN DETERMINED; I CANNOT
 15       ANSWER THAT,
 16                                MR,:HAMLIN:   Do YOU
 17       ANTICIPATE DOING  THAT,  BlLL?
 is                                MR,  TELLIARD:  No,
 19                                MR,  MEDZ:  Mo,
 20                                MR,  HAMLIN:   As I LOOKED
 21       OVER THE 600  METHODS,  IT SEEMS TO ME THAT THOSE
 22       METHODS  ARE NOT REASONABLY,,,I SHOULD SAY, THE
 23       EXPECTATIONS  OF BEING ABLE  TO INTRODUCE THOSE METHODS
24       INTO A PLANT  FOR  ROUTINE MONITORING AND COMPLIANCE
25       PURPOSES IS NOT REALISTIC,   I WOULD SUBMIT THAT THOSE

-------
 1      METHODS  WOULD  BE  SUBJECT TO SERIOUS INTERFERENCES
 2      IN A  LOT OF  PLANT APPLICATIONS,
 3            SECONDLY, IT  SEEMS  TO ME THAT THE WAY THEY ARE
 4      CURRENTLY PROPOSED,  THE GC/MASS  SPEC SYSTEM BECOMES
 5      ESSENTIALLY  THE  REFERENCE METHOD FOR .ALL THE OTHER 600
 6      PROCEDURES,  IS THAT  CORRECT?
 7                                MR, MEDZ-:   No,  SIR, THEY ARE
 8      BEING PROPOSED AS OPTIONS OF THE PERSON  WHO WANTS TO
 9      MAKE  THE MEASUREMENT,
10                                MR, HAMLIN:  STAND-ALONE
11      PROCEDURE?
12                                MR, MEDZ:   THEY ARE STAND-ALONE
13      PROCEDURES,
n                                MR, HAMLIN:  BUT IN ALL
15      INSTANCES, I BELIEVE,  YOU MAKE A STATEMENT SOMETHING
16      TO THE EFFECT  THAT IF  THERE IS A QUESTION AS TO THE
17      VALIDITY OF  THE  DATA BEING REPORTED, IT  HAS TO BE
18      CONFIRMED BY GC/MASS SPEC, IS THAT NOT CORRECT?
19                                MR, MEDZ:   ONLY IDENTITY, IF
20      THERE SEEMS  TO BE ANY  UNCERTAINTY AS TO  WHAT THE
21      IDENTITY OF  THE  COMPOUND IS FROM THE GC  RUN ITSELF,
22      THE.,,
23                                MR, TELLIARD:  THAT is THE
24      SAME  THING WE  DID OVER  THE PESTICIDE WHERE YOU HAVE SEEN
25      IT AND WE CAN  CONFIRM  IT WHEN THERE IS A MASS PROBLEM,

-------
 i                                MR,  MEDZ:   THE CONFIRMATORY
 2       TEST  CAN  BE  A SECOND COLUMN,  IT CAN BE GC/fIS, BUT IT
 3       HAS TO  BE CONFIRMED BY SOME MEANS,  IF THERE IS ANY
 4       DOUBT THAT THE PEAK COMING OFF THE  GC IS NOT ONE OF
 5       THE CONSENT  OF F.PA AGENTS,
 e                                MR,  HAMLIN:   THEN THIS LEADS
 7       BACK  INTO THE QUESTION ABOUT WHAT IS  GOING TO BE THE
 8       ROLE  OF THE  INDICATOR OF A SURROGATE  COMPOUND,
 9       INTERNAL  STANDARD OR AN INDICATOR PARAMETER,
10       YESTERDAY WHEN DEAN NEPTUNE WAS MAKING HIS DISCUSSION
11       ABOUT THE PROBLEM WITH THE PURGE AND  TRAP AND WHETHER
12       TO  INTRODUCE INTERNAL STANDARD, I THINK THERE WAS
13       SOME  COMMENT ABOUT INJECTING  IT  STRAIGHT ON THE
14       INSTRUMENT,   THAT SEEMS TO ME THAT  ONLY PROVES THE
15       PERFORMANCE  OF THE INSTRUMENT,  IT DOES NOT PROVE
16       THE METHOD,   $0 THE QUESTION  NOW IS,  IS IN THE 600
17       METHODS,  DO  YOU INTEND THAT THE SURROGATE OR
18       INTERNAL  STANDARDS   BE INJECTED IN THE FIELD, INJECTED
19       AT THE  TIME  OF SAMPLING OR INJECTED IN THE LABORATORY
20       OR  INJECTED  INTO THE INSTRUMENT?
21                                MR,  MEDZ:  THAT is ALL A
22       QUESTION  OF  THE QUALITY ASSURANCE THAT IS GOING TO BE
23       REQUIRED  ALONG WITH THE METHODS, AND  WE HAVE NOT REALLY
24       PROPOSED  ANY QUALITY ASSURANCE YET,  THE QUALITY
25       ASSURANCE PROTOCOL THAT WAS INCLUDED  IN THE PROPOSED

-------
 1       PACKAGE  IS  STRICTLY PROVIDING SOME OF OUR THINKING
 2       IN  THIS  AREA,BUT IT IS NOT MADE PART OF THE
 3       REGULATORY  LANGUAGE YET,
 4                                MR,  HAMLIN:  Is THERE NOT A
 5       QUALITY  ASSURANCE AND QC IN THE PROPOSED REGULATIONS?
 e                                F1R,  MEDZ:  THERE is A QC
 7       SECTION  IN  EACH OF  THE METHODS, BUT THAT IS A VERY,
 8       VERY  LIMITED,  VERY  MINIMAL QC THAT IS WRITTEN INTO
 9       THE METHODS THEMSELVES,
10                                MR,  HAMLIN:  So YOU ARE
11       ANTICIPATING A FUTURE PUBLICATION OF THE HA, QC TO
12       SUPPLEMENT  THE CURRENTLY  PUBLISHED AND PROPOSED 600
13       METHODS.
14                                MR,  MEDZ:  THAT WILL DEPEND
15       ON  YOUR  COMMENTS, SIR, WE ARE ASKING THE COMMUNITY,
16       THE PERSONS THAT ARE USING THESE METHODS, FOR THEIR
17       IDEAS IN THIS AREA,
is                                MR,  HAMLIN:  I WILL SUBMIT
19       THAT  IN  THE TIME SINCE PUBLICATION OF THE PROPOSED
20       METHODS  AND THE DEADLINE  FOR  COMMENTS, THERE IS NOT
21       ADEQUATE TIME TO EVALUATE IT,
22                                MR,  MEDZ:  To THAT I CANNOT
23       MAKE  A COMMENT BECAUSE THE AGENCY HAS TO MAKE THAT
24       DETERMINATION,
25                                MR,  HAMLIN:  ALL RIGHT, ANOTHER
                                  .271

-------
 1      QUESTION  I WILL ASK YOU,   I DID  NOT  SEE  ANY EVIDENCE
 2      IN THE PUBLICATION THAT SHOWED A COMPARISON OF DATA
 3      BETWEEN THE PROTOCOL GC/MASS  SPEC SYSTEM AND ANY OF
 4      THE OTHER 600 METHODS,
 5                               MR,  MEDZ:   To DATE, THAT KIND
 6      OF INFORMATION  IS JUST BEING  GENERATED,
 7                               MR,  HAMLIN:   I  WOULD ALSO
 8      SUBMIT, THEN, I WOULD LIKE TO SEE THAT TYPE OF
 9      INFORMATION BEFORE YOU CLOSE  THE COMMENT PERIOD,
10                               MR,  TELLIARD:   WE  AGREED THAT
11      THE ONLY  REPORT DATA THAT  IS  PRESENTLY AVAILABLE
12      IS THE DATA THAT HAS COME  IN  FROM CINCINNATI STUDIES
13      ON THEIR  METHODS AND WHAT  DATA YOU HAVE  ALREADY SEEN
14      FROM US ON THE  GC/MS METHODS,  As A  DIRECT  EQUIVALENCY,
15      QUOTE, EXAMINATION, NO, IT HAS NOT BEEN
16      DONE,
17                               MR,  HAMLIN:   LET ME ASK YOU
*8      THIS,  IN ESTABLISHING LIMITS OF PRECISION  IN THE
19      SURROGATE METHODS, ARE YOU PROPOSING TO  USE SAMPLES
20      IN PURE WATER,  OR SAMPLE SPIKES  IN ACTUAL AFFLUENT SAMPLE!
21      TO ESTABLISH LIMITS OF DETECTABILITY?
22                               MR,  MEDZ:   You  DO  NOT MEAN
23      SURROGATE METHODS, DO YOU, SIR,  YOU  MEAN THE
24      ALTERNATE METHODS?
25                               MR,  HAMLIN:  WELL, OKAY, THE
                                222.

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       ALTERNATE, THEN,
                                 MR,  MEDZ:   IN  THE  ALTERNATE
 3      METHODS, THE  ESTABLISHMENT  OF THE  PRECISION AND
 4      ACCURACY OF THESE  METHODS IS  A SUBJECT  OF  FOLLOW-ON
       STUDIES BY THE  AGENCY  RIGHT NOW, AND THESE  STUDIES
 6      WON'T BE COMPLETED UNTIL  THE  END OF  THIS FISCAL  YEAR,
 7                                MR,  HAMLIN:  WOULD THOSE NOT
 «      IMPACT THE VALIDITY OF THESE  METHODS?
 9                                MR,  MEDZ:   THESE  METHODS RIGHT
10      NOW  REFLECT WHAT THE AGENCY FEELS  IS THE BEST
11      REPRESENTATION  OF  THE  STATE OF THE ART  IN  MAKING THESE
12      LOW  LEVEL RESIDUE  ANALYSES  FOR THE CONSENT  DECREE
13      POLLUTANTS,   WHAT  WE WANT TO  DO RIGHT NOW  IS TO
       ESTABLISH THAT  WITHIN  THE ENTIRE COMMUNITY, RESEARCH
15      COMMUNITY, THE  REGULATED  COMMUNITY,  THAT WE HAVE
16      GOT  A GOOD FIRST APPROXIMATION OF  THE STATE OF THE
17      ART,
                                 MR,  HAMLIN:   I DO  NOT THINK  •
19      YOU  HAVE DEMONSTRATED  THAT UNLESS  YOU CAN  SHOW THE
"0      COMPARISON BETWEEN THE RESULTS USING THESE  METHODS
21      AND  THE METHOD  USED IN THE VERIFICATION PROCEDURE.
22                                MR,  MEDZ:   THE COMPARISON
23      THAT WE WILL  HAVE  INITIALLY IS'WE  WILL  HAVE PRECISION
24      AND  ACCURACY  STATEMENTS ON THE TWO METHODS  APPLICABLE
25      TO SPECIFIC DISCHARGES,   THAT WILL NOT  BE  THE  KIND OF
                               .221.

-------
 1       INFORMATION  WE  GENERATE  FROM INTERLABORATORY,



 2       COLLABORATIVE TESTING, BUT IT WILL BE A FIRST



 3       APPROXIMATION AS  TO  THE  COMPARABILITY OF THE TWO



 4       METHODS.



 5                                MR,  HAMLIN:   I WON'T BELABOR



 6       THE  POINT; YOU  HAVE  NOT  CONVINCED  ME  TOTALLY ABOUT



 7       THAT,



 8            IN THE  PROPOSED CONSOLIDATED  PERMIT REGULATIONS



 9       WHICH THIS KIND OF RELATES TO,  YOU HAVE STATED SOMETHING



10       TO THE EFFECT THAT, IF THERE WAS NO KNOWLEDGE AS TO



11       REAL DISCHARGE  LEVELS OF POLLUTANTS, THAT A PERMIT



12       CONDITION OF FIVE TIMES  THE DETECTION LIMIT COULD



13       BE IMPOSED ON THE PERMIT,   THE  QUESTION I  AM ASKING



14       NOW  IS, WHAT IS BEING USED TO ESTABLISH DETECTION



15       LIMITS?



IB                                MR,  MEDZ:  AT THE PRESENT TIME,



17       THE  ONLY APPROXIMATION WE HAVE  OF  DETECTION LIMITS



18       OF THESE METHODS  ARE THOSE DETECTION  LIMITS THAT WERE



19       DETERMINED BY THE CONTRACTORS USING THESE  PROCEDURES



20       IN REAL WORLD SAMPLES, RECOVERIES  FROM RELATIVELY



21       CLEAN DISCHARGE WATERS,  BUT THEY ARE  TREATED



22       EFFLUENTS,   NOW AS FAR AS THAT  CONSIDERATION THAT



23       YOU  HAVE JUST DISCUSSED  ON THE  COMBINED PERMITS FORM



24       REGULATION,  I DO  NOT KNOW WHAT  THE FINAL FORM OF THAT



25       IS GOING TO  BEj I DO NOT KNOW IF THAT REQUIREMENT WILL
                                 .224.

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1       CARRYOVER  INTO THE FINAL REGULATION OR NOT,  SOME
2       FORM OF IT PROBABLY WILL, BUT  I DON'T KNOW EXACTLY
3       WHAT THE FORM OF THAT WILL BE  IN THE FINAL REGULATION,
4         DETECTION LIMIT, I THINK, STILL BECOMES AN
5       EXTREMELY CRITICAL QUESTION ANY TIME WE'RE USING
6       ANY OF THESE ANALYTICAL METHODS, AND I THINK IT  IS
7       TIME, I THINK THE STATE OF THE ART WILL ALLOW US
g       TO START PROVIDING LANGUAGE BY WHICH THE DETECTION
g       LIMIT CAN BE DETERMINED, DEFINED AND DETERMINED
10       EXPERIMENTALLY,  IN ORDER TO INTERACT WITH THE
n       PERSONS THAT HAVE TO USE THIS METHOD, TO FIRM UP
12       WHAT THE DETECTION LIMITS OF THIS METHOD  ACTUALLY
13       ARE,  IN THE NEXT PACKAGE WE INTEND TO PROPOSE A
14       DEFINITION AND EXPERIMENTAL PROCEDURES BY WHICH
15       DETECTION LIMIT MIGHT BE DETERMINED.  As I SAY,
16       THIS IS PROPOSED,  JUST LIKE THE DECEMBER 3RD
17       PACKAGE IS PROPOSED, IT'S NOT A FINAL REGULATION
is       YET,  IT WON'T BE FINAL UNTIL WE GET ALL YOUR COMMENTS
19       AND  EVALUATE THE COMMENTS AND MAKE CERTAIN THAT
20       OUR DATA BASE ADEQUATELY DEFINES THE STATE OF THE
21       ART AND THESE METHODOLOGIES,
22                                ilR, HAMLIN:  WELL, WHAT I'M
23       CONCERNED ABOUT IS,I NOTICE IN THE STATEMENT AS TO
24       THE  PRECISION FOR THE BOD METHOD, THAT STATEMENT IS
25       BASED UPON THE STANDARD OF GLUCOSE AND GLUTAMIC
                                  _275_

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1       STANDARD,   I  WOULD SUBMIT THAT THE UNCERTAINTY OF
2       REAL SAMPLES  IS MUCH,  MUCH GREATER THAN THAT OF THE
3       STANDARD, AND  TO ALLUDE THAT THE PRECISION OF THE
4       METHOD IS EQUAL TO THE STANDARD, I THINK,IS
5       INACCURATE.   I  THINK THAT ANY METHOD SHOULD BE AND
6       CERTAINLY THE METHOD SHOULD BE BASED UPON THE
7       PERFORMANCE BASED ON REAL SAMPLES AND NOT IDEAL
8       STANDARDS OR  SAMPLES INJECTED IN JUST PLAIN WATER,
9         IF YOU DON'T MIND, I'D JUST LIKE TO GO OFF, VERY
10       BRIEFLY, ON  THE 600 METHODS AND MAKE A GENERAL
11       COMMENT ABOUT SOME OF THE THINGS WE TALKED ABOUT
12       YESTERDAY EVENING,  As NEAR AS I CAN TELL, I
13       HAVEN'T SEEN  ANY EVIDENCE OF THE AGENCIES ATTEMPTING
14       TO SEPARATE  SAMPLING ARTIFACTS DATA FROM COMPOUND
15       OCCURRENCE IN EFFLUENT SAMPLES,  ONE OF OUR
16       EXPERIENCES  HAS BEEN THAT WE WERE SAMPLED LAST
17       SUMMER AND SPLIT SAMPLES WITH THE CONTRACTOR,  THEY
18       REPORTED TOLUENE AS PRESENT IN OUR EFFLUENT,  WE
19       HAVE SUBSEQUENTLY RESAMPLED AND WE ALSO DETECTED
20       TOLUENE IN ONE OF OUR SAMPLES WHERE WE TRACED IT
21       TO THE FACT THAT THE PERSON TAKING THE SAMPLE WORE
22          A PAIR OF RUBBER GLOVES,  WHAT I'M SUGGESTING
23       HERE IS THAT YOU HAVE A LOT OF DATA THAT HAS
24       ARTIFACT INFORMATION BASED UPON THE SAMPLING
25       TECHNIQUES THAT WERE USED  IN SECURING THE SAMPLES,
                                 276

-------
1        AND I SUGGEST THAT THE AGENCY CONSIDER  SENDING BACK
:       A QUESTIONNAIRE TO THE COMPANIES THAT WERE TESTED
3       AND SAMPLED DURING THE VERIFICATION PROCEDURES TO
4       ASK SIMPLY., ARE THE COMPOUNDS LISTED REASONABLY
5       GENERATED BY YOUR PROCESS, TO SEPARATE OUT THOSE
6       COMPOUNDS THAT ARE A RESULT OF THE MANUFACTURING
7       PROCESS AND POSSIBLE CONTAMINATION THROUGH  SAMPLING,
8       WHATEVER  IT IS,   I THINK  THAT WOULD BE  A REASONABLE
9       RESPONSE,
10         ALSO,  I'D LIKE  TO REITERATE THAT ANY  STANDARD BE
11       A TEST OF THE METHOD AND  NOT THE  PERFORMANCE  OF THE
12       INSTRUMENT AND  I  THINK THAT'S REALLY  IMPORTANT,
13       THANK YOU,
14                                 MR, MEDZ:  THANK YOU,
15                                 MR, MARKS:  DAVE MARRS,
is       STANDARD  OIL,   DR, MEDZ,  BILL TELLIARD  INDICATED
17       THAT WE  COULD ASK FOR ANYTHING BUT AN EXTENSION;
is       THAT'S BEEN ASKED FOR,  I  THINK; BUT COULD YOU
19       ENLIGHTEN  US A  LITTLE BIT OF WHETHER,,.WHAT TIME-
20       TABLE THE  AGENCY  IS  LOOKING AT TO PROMULGATE  THESE
21       METHODS?
22                                 MR, MEDZ:  THE TIME-
23       TABLE OF  THE AGENCY,  THE  PERMITS  APPARATUS  WANTS
24       TO  RENEW THE PERMITS  STARTING  IN  THE  APRIL  TIME
25       FRAME,   THIS REGULATION  IS  EXTEMELY  IMPORTANT TO
                                   277

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 1       THAT ACTIVITY AND THE AGENCY WOULD  LIKE  VERY  MUCH
 2       TO HAVE THESE REGULATIONS  IN PLACE  BY  THEN,   I'M
 3       COMMITTED TO THAT,
 4                                MR, MARRS:  NOT BEING A
 5       LAWYER^   I DON'T UNDERSTAND THE  INS AND  OUTS  OF THE
 6       CLEAN WATER ACT REAL WELL, BUT COULD YOU EXPLAIN A
 7       LITTLE BIT ABOUT, OR MAYBE SOMEONE  ELSE  IN THE AGENCY,
 8       ABOUT THE USES THAT ONCE THESE METHODS ARE PROMULGATED
 9       THEY WILL HAVE IN TERMS OF COMPLIANCE  MONITORING
10       AND ENFORCEMENT?
11                                MR, MEDZ:  IF THESE  METHODS
12       ARE APPROVED IN A FORM SIMILAR TO WHAT THEY ARE
13       RIGHT NOW, THEN THAT WILL DEPEND UPON  YOUR COMMENTS,
14          I CAN'T  ASSURE YOU THAT THEY'LL STAY THE  WAY THEY
15       ARE BECAUSE I HAVEN'T SEEN ALL OF YOUR COMMENTS YET;
16       BUT ASSUMING YOUR COMMENTS DO NOT DRASTICALLY CAUSE
17       THE AGENCY TO CHANGE THOSE METHODOLOGIES, THOSE
18       METHODOLOGIES WILL BE THE LEGAL METHODS  BY WHICH A
19       DISCHARGER HAS HIS OPTION OF MAKING HIS  MEASUREMENTS
20       TO SHOW COMPLIANCE, AND THE METHOD,  THEN, THAT WILL
21       HAVE TO BE SHOWN BY THE ENFORCEMENT PEOPLE WHO
22       NEED TO BE THE ONE THAT THE DISCHARGER HAS SELECTED
23       TO USE,  WE RECOGNIZE WHEN YOU'RE TALKING ABOUT PARTS
24       PER BILLION, THERE ARE NO TWO METHODS  THAT WILL GIVE
25       YOU IDENTICALLY THE SAME RESULTS; WE RECOGNIZE THIS;
                                  278

-------
  1       BUT WE HAVE TO GET AS GOOD AN APPROXIMATION OF THE
  2       STATE OF THE ART RIGHT NOW THAT WILL ALLOW THE
  3       DISCHARGER AND THE ENFORCER TO USE THE SAME YARDSTICK
  4       TO MEASURE THE DISCHARGE,AND WE THINK WE'VE COME
  5       UP WITH A PRETTY GOOD APPROXIMATION OF THE STATE OF
  6       THE ART TO BE ABLE TO DO THIS,  YOUR COMMENTS MIGHT
  7       CHANGE OUR MINDS, I DON'T KNOW,
  s                                MR,  MARKS:   I WOULD HOPE
  9       so,
 10                                MR, BLOOM:  SAUL BLOOM,
 11       EXXON RESEARCH,  YESTERDAY WE HEARD THE INVESTIGATORS
 12       DESCRIBING MICROEXTRACTION, AND IN THE COURSE OF
 13       QUESTION AND ANSWER PERIOD,  THE INVESTIGATORS
 14       ACKNOWLEDGED THE FACT THAT THE WORK WAS STILL IN THE
 15       RESEARCH AND DEVELOPMENT PHASE.  THIS MORNING WE
 16       HEAR THE AGENCY  INTENDS TO PROPOSE THIS IN THE SECOND
 17       PACKAGE AS A METHOD, AND MY QUESTION IS, IS IT THE
 18       POSITION OF THE 304 H COMMITTEE TO RECOMMEND TO THE
 19       AGENCY TO PROMULGATE METHODS THAT ARE STILL IN THE
 20       R AND D PHASE?
 21                                MR, f€DZ:  ONE OF THE THINGS
 22       WITH WHICH WE ARE EXTREMELY CONCERNED IS COST OF
 23       ANALYSIS TO THE REGULATED COMMUNITY,  IF THERE APPEAR
 24       TO BE ADVANTAGES, COST ADVANTAGES TO THE DISCHARGER;
2.5       IN USING SUCH A PROCEDURE AS A MICROEXTRACTION
                                   279

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1        TECHNIQUE,  AND IF WE FEEL THAT THE PRECISION AND
2        ACCURACY OF THE DATA THAT'S GENERATED FROM THAT
3       PROCEDURE WILL BE SUFFICIENT IN ACCURACY AND
4       PRECISION TO MAKE CERTAIN THAT THE AGENCY INTERESTS
5       ARE PROTECTED, THEN WE WOULD PROPOSE SUCH A
6       PROCEDURE FOR CONSIDERATION, STRICTLY BECAUSE IT
7       WILL GIVE A COST BENEFIT TO THE DISCHARGER,
8         AGAIN, THE METHOD WILL BE PROPOSED AND IT WILL
9       NOT BE MADE A FINAL APPROVED METHOD WITHOUT BEING
10       DEVELOPED TO THE EXTENT WHERE TECHNICALLY IT CAN
11       GIVE A PRECISION AND ACCURACY WHICH THE ENFORCEMENT
12       AND PROGRAMATIC INTERESTS OF THE AGENCY REQUIRE,  I
13       DON'T KNOW, DOES THAT ANSWER YOUR QUESTION?
14                                MR, BLOOM:  WELL, I GATHER
15       THAT WHAT YOU'RE SAYING IS THAT IF IT LOOKS PROMISING
16       AND IT LOOKS COST-EFFECTIVE, THEN IT WILL BE PROPOSED,
17       EVEN THOUGH IT'S INCOMPLETE,
is                                FIR, MEDZ:  THAT'S RIGHT,
19                                MR, BLOOM:  THANK YOU,
20                                MR, CLAEYS:  BOB CLAEYS FROM
21       THE (NATIONAL COUNCIL,  WE'RE A LITTLE BIT CONFUSED
22       THAT THESE ARE PROPOSED METHODS-.  YOU'RE GOING TO
23       ASK FOR COMMENTS, AND THEN  IT SOUNDS LIKE THEY'LL
24       BECOME FINAL METHODS,  Do WE GET THE COMMENT AGAIN ON
25       THE FINAL METHOD, BECAUSE  I SUBMIT RIGHT NOW THESE
                                   280

-------
 1       PROPOSED METHODS ARE AT BEST, AS WRITTEN  IN THE DECEMBER
 2       3RD REGISTER, THEY'RE  so POORLY WRITTEN THAT  THERE'S
 3       A LOT OF DISTANCE BETWEEN  THESE PROPOSED METHODS  AND
 4       WHAT MAYBE COME OUT AS FINAL METHODS,  $0 WILL WE
 5       HAVE A CHANCE TO COMMENT ON THE, QUOTE, FINAL  METHOD?
 6                                MR, MEDZ:   No,  You  CAN
 7       COMMENT ON IT, BUT WE  WILL PROBABLY,,,WE WON'T REPROPOSE,
 *       IF THAT'S WHAT YOUR QUESTION is,
 9                                FIR, LICHTENBERG:  JIM
10       LICHTENBERG, EPA,  I JUST  WANT TO MAKE A COUPLE OF
11       COMMENTS WITH REGARD TO SOME OF THE  QUESTIONS THAT
12       HAVE BEEN RAISED,  ONE, YOU KNOW, THE MICROEXTRACTION
13       PROCEDURE WHICH WAS PRESENTED YESTERDAY,  THAT IS
14       NOT GOING TO BE PROPOSED AS AN ACROSS-THE-BOARD
15       APPLICATION,  IT'S BEING PROPOSED ON A VERY LIMITED
16       BASIS FOR THOSE APPLICATIONS WHERE  IT HAS BEEN USED
17       AND SHOWN TO WORK IN A PARTICULAR INSTANCE,   IT'S
18         NOT PROPOSED ACROSS-THE-BOARD,  THAT SAME GOES
19       FOR THE REST OF THE METHODS INVOLVED THAT ARE NOT
20       THE 600 SERIES METHODS.  THEY ARE BEING OR WILL BE,
21       I UNDERSTAND, PROPOSED AS  METHODS TO BE USED  OR THAT
22       MAY BE USED  IN THOSE SPECIFIC AREAS  WHERE THEY HAVE
23       BEEN USED IN THE PRELIM-INARY WORK AND HAVE DATA TO
24       SUPPORT THEM  IN THE PROGRAMS THAT HAVE BEEN USING
25       THEM,  IN TERMS OF THE INTERLABORATORY STUDIES THAT
                                    281

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 1       ARE GOING ON, WE ARE LOOKING AT A WHOLE  CROSS  SECTION
 2       OF SAMPLE TYPES FROM THE CLEANEST WATER  TO
 3       REPRESENTATIVE WASTE EFFLUENTS IN THE  INTERLABORATORY
 4       STUDIES GOING ON,  THERE ARE 20 LABORATORIES,  MINIMUM,
 5       PARTICIPATING IN THESE STUDIES AND  THEY  ARE  A  CROSS
 6       SECTION OF LABORATORIES UNDER CONTRACT; SO WE ARE
 7       LOOKING AT PROPER SAMPLE TYPES WITHIN  EACH  INDIVIDUAL
 8       METHOD,  WE DO HAVE ONGOING, IN OUR SHOP, ANALYTICAL
 9       INVESTIGATIONS IN TERMS OF ACCURACY AND  PRECISION
10       WITH THE 624 AND 625 METHODS AND AN INTERLABORATORY
11       STUDY  IS PLANNED FOR THOSE AS WELL.
12         OTHER AREAS, THE METALS ANALYSIS  AREAS, THERE  is
13       ALSO WORK GOING ON IN OUR SHOP IN THOSE  AREAS,   I
14       JUST WANTED TO TRY TO MAKE A FEW POINTS  OF  CLARIFICATION,
15                                MR, HOCHGESA.JG:  MY NAME  is
is       FRANK  HOCHGESANG, I'M WITH MOBIL  OIL  COMPANY,   I  HAPPEN
17       TO ALSO BE CHAIRMAN OF AN ANALYTICAL  TASK FORCE WITHIN
is       THE AMERICAN PETROLEUM INSTITUTE,   I'M TRYING  TO
19       CONTINUE, JUST A LITTLE, THE DISCUSSION  THAT'S BEEN
20       GOING  ON, BUT I'D LIKE TO RESTRICT  MY  COMMENTS TO  METHODS
21       624 AND 625,  THOSE GC/MS METHODS ARE  THOSE  THAT HAVE
22       BEEN USED IN THE REFINERY SURVEY COLLECTING  OF DATA
23       BASE AND THEY HAVE BEEN THE STATE OF  THE ART,  THE  BEST
24       THAT COULD BE DONE, AND BOTH INDUSTRY  AND EPA HAVE
25       WORKED TOGETHER TO TRY TO GET THE MOST VALID NUMBERS
                                  282

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 1        POSSIBLE.   WHAT  CONCERNS  ME is  THAT WE HAVE,  OVER THE
 2        PAST  YEAR  OR  SO,  DEVELOPED SOME INFORMATION THAT
 3        GENERALLY  SEEMS  TO  BE  TECHNICALLY VALID WHICH INDICATES
 4        CONSIDERABLE  ANALYTICAL  UNCERTAINTY BETWEEN LABORATORIES.
 5        EXPERIENCED LABORATORIES, WHEN THESE METHODS ARE
 6        APPLIED AND IN MY CASE,  THE PETROLEUM WASTEWATERS,
 7        THAT  UNCERTAINTY  is IN THE RANGE OF 10 TO  50 MICROGRAMS
 8        PER LITER.  SO MY CONCERN IS WE'RE ADVANCING  FROM
 9        COLLECTING THE DATA BASE,  IN MY OPINION, TO A COMPLIANCE
10        MONITORING AND POTENTIAL  ENFORCEMENT PROBLEMS AND
11        WITHOUT HAVING ESTABLISHED WHAT THE INTERLABORATORY
12        REPRODUCIBILITY  OF  THESE  THINGS IS,  IT JUST SEEMS TO
13        BE, HOW SHALL I  SAY IT,  OPENING UP A WHOLE SITUATION
14        OF TURMOIL.   I WONDERED  IF YOU  HAD ANY COMMENT ABOUT
15        THE HOW, THE  RESULTS OF  THESE TESTS THAT WILL BE
16        APPLIED NOW IN THE  NEAR  FUTURE, LIKE IN NPDS  PERMIT
17        APPLICATIONS  AND  PERMIT  WRITERS'SETTING, THEN THE
18        CONTROL LIMITS,  ANY COMMENT YOU MIGHT MAKE ABOUT THE
19        ANALYTICAL REPRODUCIBILITY, ESPECIALLY OF THOSE METHODS
20        WHICH HAVE BEEN  MOST WIDELY USED,
21                                 MR, TELLIARD:   FRANK,   WE
22        HAVE  ON THE STREET  PROPOSED REGULATIONS FOR THE
23        PETROLEUM  INDUSTRY.  WHAT ARE THE PARAMETERS  FOR
24        REGULATING, FRANK,   PHENOL,  CHROME;  ALL RIGHT,   WE'VE
25        GOT METHODS FOR  PHENOL AND CHROME, FRANK,   WE DIDN'T
                                 283

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1       GIVE YOU 1, 2-DIPHENYL BAD STUFF, WE DIDN'T  PUT  THAT
2       ANYWHERE IN THE REGULATION,  SAMARIUM WAS  NOT  IN
3       THERE., WE DO NOT INTEND TO REGULATE THAT,  ANYTHING
4       WE PUT IN THAT REGULATION WE HAD DATA ON AND WE  HAD
5       A PROVEN METHOD FOR,  NOW YOU CAN ACCUSE ME, I'M
6       SURE YOU'RE GOING TO SEND IN YOUR COMMENTS DURING
7       THIS COMMENT PERIOD, THAT YOU WANT ME TO ADD  PHENOL,
8       YOU WANT ME TO ADD XYLENE, TETRAETHYL LEAD AND A FEW
9       OTHER PARAMETERS, YOU'D FEEL BETTER, RIGHT, YOU'RE
10       GOING TO DO THAT,  THE INDUSTRY IS GOING TO  TELL ME,
11       GIVE US MORE PARAMETERS,
12                                MR, HOCHGESANG:   BILL,  YOU
13       HAVE A WAY OF COMING BACK WITH A VERY PERTINENT  COMMENT,
14                                MR, TELLIARD:  I  THINK  THAT
15       WAS A TRANSLITERAL TRANSIT OF A STICK IT IN YOUR EAR, BUT
16       GO AHEAD,
17                                MR, HOCHGESANG:   WELL,  TO TRY
18       TO RESPOND, WE HAVE WORKEDCOLLECTIVELY AND  FOUND  THAT'
19       THERE'S NO NEED TO  PUT ADDITIONAL PARAMETERS OF
20       SPECIFIC TOXICS AND PETROLEUM,  HOWEVER,  I'M STILL
21       CONCERNED THAT THESE METHODS AREN'T GOING  TO BE  USED
22       TO FURTHER COLLECT  THE DATA BASE AND THAT  WAS  IN THE
23       NATURE OF THE QUESTION THAT I HAD PUT OUT  TO SEE IF
24       ANYONE CAN COMMENT  AT THE MOMENT,   I THINK IT'S
25       A DIFFICULT SITUATION, BUT WE'RE ALL  IN IT,
                                   284

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 i                                MR, TELLIARD:  WELL,  I  THINK
 ?       THAT, YOU KNOW, WE HAVE CONTINUALLY  SAID THAT  IF WE'RE
 3       GOING TO PUT A NUMBER  IN A REGULATION, WHETHER  IT BE
 4       SAMARIUM OR BOD, WE'LL HAVE THE DATA  FOR IT,   NOW,
 5       WE HAVE ALSO IN THE PREAMBLE,PETROLEUM  POINTED OUT THE
 6       FACT THAT, YES, WE'RE GOING TO PICK  OUT A  COUPLE OF
 7       REFINERIES, WE'RE GOING TO GO OUT THERE AND WE'RE GOING
 8       TO SAMPLE LONG TERM WITH THESE METHODS  AND GENERATE
 9       SOME DATA THAT MAY OR MAY NOT BE USABLE,   WE RECOGNIZE
10       THAT THERE'S CERTAIN LIMITATIONS WITHIN ALL OF THIS
11       STUFF,  WE'VE BEEN FIGHTING OVER THIS NOW  FOR  TWO YEARS,
12       WORKING TOGETHER, PULLING IT TOGETHER AND, YOU KNOW,
13       WE STARTED FROM 0,  So  YES, WE'RE GOING TO GO LOOK AT
14       PETROLEUM REFINING WITH METHODOLOGY,  AND IF THE METHODS
15       AREN'T ANY GOOD AND THE DATA ISN'T ANY  GOOD,WE'RE NOT
16       GOING TO USE IT,SIMPLE ENOUGH,
17                                MR, HOCHGESANG:   FAIR ENOUGH,
is                                MR, MA'RR'S:.  BILL, JUST TO  .
19       FOLLOW UP AND THIS IS DAVE MARRS, STANDARD OlL.   JUST
?0       TO FOLLOW UP ON THAT,  THE CONCERN FOR  THESE METHODS
21       GOES BEYOND THE EFFLUENT GUIDELINES,  FlRST OF ALL,  IN
22       THE EFFLUENT GUIDELINES YOU DID MENTION THAT YOU ARE
23       ALSO LOOKING AT ETHYL BENZENE, BENZENE  TOLUENE,  AND A
24       COUPLE OF OTHERS, BUT  IN ADDITION THESE METHODS, ONCE
25       THEY BECOME PROMULGATED, WILL BECOME APPLICABLE  FOR  USE
                                   285

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 1       BY THE STATES AND WITH ALL DUE RESPECT  TO  THE  STATE
 2       ERA'S THAT  I HAVE DEALT WITH, THESE  PEOPLE  ARE  LIGHT-
 3       YEARS BEHIND THE PEOPLE IN THIS ROOM IN TERMS OF
 4       ORGANIC ANALYSIS, AND I THINK THAT, YOU KNOW,  IN TERMS
 5       OF WHAT YOU'RE DOING, OKAY, MAYBE YOU  CAN GET BY
 6       WITH IT; BUT BY PROMULGATING THESE METHODS  AND  GIVING
 7       THEM THE FORCE OF LAW, YOU ARE ESSENTIALLY  OPENING
 8       THEM UP TO  PEOPLE WHO MAY OR MAY NOT BE ABLE  TO USE
 9       THEM AND THINGS MAY GET OUT OF CONTROL,
10                                MR. TELLIARD:  THIS  GOES
11       BACK TO THE SYNDROME OF, YOU KNOW, GUNS DON'T KILL
12       PEOPLE, PEOPLE KILL PEOPLE, AND THAT'S WHY WE  HAVE
13       POLICEMEN;  I CAN'T ANSWER THAT,  TRUE, THE  AGENCY IS
14       TAKING ITS  BEST SHOT AT A RATHER HARD QUESTION  IN
15       ANALYTICAL  CHEMISTRY, BUT YOU CAN RUN BOD'S,  PH'S
16       AND NEVER GROW IN KNOWLEDGE, AND I DON'T THINK WE WANT
17       TO DO THAT,  EITHER,  SOMEONE SAYS MAYBE THE  RATE OF
1«        GROWTH IS  A LITTLE BIT EXTRAPOLATED AND  PERHAPS IT
19       is,  WE DON'T DENY THAT; BOB is UP TO  HIS BEHIND WITH
20       ALLIGATORS  AND WE'VE GOT SOME HARD QUESTIONS  AND
21       WE'RE TRYING TO GIVE IT OUR BEST SHOT,  I THINK BEING
22       REALISTIC,  THE COMMENTS WE RECEIVE FROM YOU GIVE  US
23       A LEATHER  TOY TO GO WITH OUR MANAGEMENT  WITH AND SAY
24       WELL,  MAYBE WE OUGHT TO  EXTEND  IT;  MAYBE  WE OUGHT  TO
25       DO SOMETHING HERE,   I THINK THE  COMMENTS ARE IMPORTANT
                                    286

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1       FROM THIS COMMUNITY BECAUSE YOU'RE THE  MOST  KNOWLEDGEABLE
2       AT IT,  WHEN  I SAID COMMENTS, TELLING us  WE'RE  DUMB,
3       I MEAN  I DON'T MIND YOU OPENING  THAT WAY;  BUT  IF  YOU'D
4       PUT SOME MEAT INTO  IT  LIKE A NUMBER OR  TWO,  OR  SOME
5       DATA, JUST SENDING  US  A LETTER SAYING WE'RE  DUMB  REALLY  ;
6       DOESN'T HELP  us TOO MUCH,  I MEAN, THAT'S  WHERE YOU
7       GET THE ONE-LINER BACK, THANK YOU.
s                                MR, MEDZ:  THANK  YOU,  BILL.
s                                MR, TELLIARD:  THANK YOU, BOB,
10                                (APPLAUSE,)
11                                MS, WARNER:  MY  NAME  is  BEV
12       WARNER  FROM MONSANTO RESEARCH IN DAYTON,   YOU'VE  HEARD
13       THEM TALK ABOUT THE 600 METHODS  601 THROUGH  613,  AND
14       YOU'VE  HEARD  MR,  LlCHTENBERG MENTION THE  VALIDATION
15       STUDIES, THE  INTERLABORATORY VALIDATION STUDIES,   I
16       HAPPEN  TO BE  PRINCIPAL INVESTIGATOR FOR INTERLABORATORY
17       VALIDATION STUDYJ WE'RE GOING TO BE STARTING ON SOME
18       OF THESE METHODS,   THAT'S 601, 602, 603,  AND 613  AND
19       WITHIN  THE NEXT TWO WEEKS OR SO, I'LL BE SENDING OUT BID
20       PACKAGES,  SO IF  ANY OF YOU ARE  INTERESTED,  YOU CAN
21       CALL ME AT MONSANTO AND  I'LL SEND YOU OUT AND YOU CAN
22       GET A CHANCE  TO BID ON PARTICIPATING  IN THIS AND  YOU
23       CAN GET YOUR  COMMENTS  BACK TO THE EPA THROUGH ACTUALLY
24       DOING THE SAMPLES, AND  IF YOU'RE  NOT REALLY FAMILIAR
25       WITH THE PROGRAM,  IT STARTS OUT  WITH TWO  TEST  SAMPLES
                                  287

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 1       TO TRY OUT THE METHODS, JUST TO BECOME FAMILIAR WITH
 2       THE METHODS AND WITH THE INSTRUMENTATION,AND ONE
 3       THAT WE'RE GOING TO BE SENDING OUT WILL BE,,,WE'LL
 4       BE SENDING OUT AMPULES THAT YOU'D SPIKE WATER WITH,
 5           ONE WILL BE SPIKED IN DISTILLED WATER AND ONE
 6       WILL BE AN EFFLUENT WATER THAT MOST LIKELY HAS THE
 7       PROPOSED COMPOUNDS IN  IT,  YOU TRY OUT THE METHOD
 8       WITH THAT, WORK AROUND WITH IT, AND THEN EPA IN
 9       CINCINNATI WILL HOLD A MEETING WITH EVERYBODY THAT
10       PARTICIPATES IN IT,  YOU GET TO AIR YOUR GRIPES,  AIR
11       THE PARTS OF THE METHOD THAT YOU DON'T THINK WORKS,
12       WE'LL WORK ON  IT, TRY  TO WORK  IT OUT AND THEN WE'LL
13       SEND OUT THE ACTUAL METHOD SAMPLES,  THESE WILL BE
14       DISTILLED WATER FROM YOUR LAB, ONE SURFACE WATER,
15       ONE DRINKING WATER, AND THREE  EFFLUENT WATERS FOR
16       EACH CATEGORY,  So IF  YOU'RE INTERESTED AND YOU REALLY
17       WANT TO AIR,,,YOU WANT TO GET  PAID FOR PLAYING AROUND
18       WITH THESE METHODS TO  SEE WHAT THEY'RE LIKE, WRITE
19       ME AT MONSANTO OR CALL ME AT MONSANTO AND I'LL BE GLAD
n°       TO SEND YOU OUT THE PACKAGES.
21                                MR. TELLIARD:  THANK YOU,
22       SINCE WE'VE RESOLVED ALL OUR ANALYTICAL PROBLEMS  IN
23       ANALYZING WATER SAMPLES., WE THOUGHT WE WOULD MOVE ON
24       TO ANALYZING SLUDGES)  SOME SORT OF A CHALLENGE SINCE
25       THIS STUFF  IS  ALL DONE NOW AND JoAN  FlSK, WHO PRESENTLY
                                288

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1         WORKS FOR VYER,  is  GOING  TO TALK TO YOU ABOUT A
2         PROPOSED PROTOCOL FOR  THE MEASUREMENT OF OUR
3        PRIORITY POLLUTANTS IN SLUDGES,   THE METHOD THAT
4        IS BEING PROPOSED HERE, WE WILL  HAVE COPIES OF
         IT AND WE'LL  LEAVE  IT  OUT ON THE TABLE AGAIN AS
6        YOU LEAVE  IF  YOU WANT  TO  PICK UP A COPY,
7
8
9
10
11
12
13
14
15
16
17
18
19
21
22
23
24
25

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290

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 i                 PRELIMINARY METHODS FOP  ORGANIC
 2                AND ELEMENTAL ANALYSIS  OF SLUDGES
 3                          BY:  JOAN FISK
 4
 5             I'M NOT SURE THERE'S AN APPROPRIATE TIME OF DAY
 6       TO TALK ABOUT SLUDGE BECAUSE I DON'T THINK ANYBODY
 7       LIKES TO THINK ABOUT IT, ESPECIALLY BEFORE LUNCHTIME,
 8             IT'S AN OBVIOUS CONCERN IN  THE ESTABLISHMENT AND
 9       IMPLEMENTATION OF EFFLUENT GUIDELINES TO GATHER
10       INFORMATION ON THE NATURE OF THE CONSERVATISM OF
11       POLLUTANTS,  VIE MUST DISCOVER WHAT POLLUTANTS
12       ARE DESTROYED BY TREATMENT SYSTEMS AND WHICH ARE
13       TRANSFERRED FROM ONE MEDIA TO ANOTHER; THAT IS, FROM
14       THE WASTEWATER DISCHARGE TO RESIDUAL WASTE, WHICH
15       WE SHALL DESCRIBE BY THE ALL-ENCOMPASSING TERM,
16       'SLUDGE,'  THE SLUDGES FROM BOTH INDUSTRIAL AND
17       POTW  SOURCES ARE ULTIMATELY DISPOSED OF EITHER IN
18       STORAGE DRUMS OR LANDFILLS—THEIR  IMPACT ON THE
19       ENVIRONMENT, UNKNOWN, WITHOUT KNOWLEDGE OF THEIR
20       POLLUTING OR HAZARDOUS NATURES,  A.NY METHODOLOGY
21       DEVELOPED FOR ANALYSIS OF SLUDGES  AND INFORMATION
22       OBTAINED BY THESE METHODS WILL ALSO BE INSTRUMENTAL
23       IN AIDING THE PROGRAMS OF THE OFFICE OF SOLID
24       WASTE, WHICH GO HAND IN HAND WITH  OUR OWN MISSIONS,
25       ANALYSES  WILL  BE  REQUIRED FOR  THE CONSTITUENTS
                                 291

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1       OF  THE  SOLID  WASTES  BEFORE MOBILITY AND SOIL
2       ATTENUATION STUDIES  CAN OCCUR,
3         I  WILL ATTEMPT TO  DESCRIBE THE PROTOCOL DEVELOPED
4       BY  MIDWEST RESEARCH  INSTITUTE IN KANSAS CITY,   IT'S
 5       PROBABLY GOING  TO SOUND A LITTLE LIKE ED HERLIHY
6       AND HIS RECIPES  FROM THE KRAFT KlTCHEN AND YOU'LL '
7       HAVE TO PARDON  THAT,   THIS PROTOCOL, FOR EXPEDIENCY'S
8       SAKE, WAS DESIGNED AROUND THE EXISTING SAMPLING
9       AND ANALYSIS  METHODS FOR WASTEWATER, WITH APPROPRIATE
10       MODIFICATIONS WHEN NECESSARY, OF WHICH THERE WERE
n       MANY,  SINCE  YOU SHOULD ALL BE  FAMILIAR WITH THE
12       304H METHODS, I'LL EMPHASIZE THE CHANGES AND ADDITIONS
13       THAT ARE ESSENTIAL DUE TO THE DIFFICULT MATRIX THAT
14       SLUDGE  IMPARTS,   I MIGHT MENTION ALSO, AT THIS
15       POINT THAT THE  METHOD HAS BEEN  ADAPTED FOR POTW
16       SLUDGES ONLY, AND ALL THE RECOVERY DATA THAT WE
17       POSSESS  IS  FOR THESE SAMPLES,   WE DO NOT PRESENTLY
18       HAVE INFORMATION AS TO THE APPLICABILITY OF THE
19       METHODS TO INDUSTRIAL SLUDGES, THOUGH WE CAN PREDICT
20       THAT SOME INDUSTRIES WILL PRESENT PROBLEMS,
21       HOPEFULLY, THEY WILL BE TAKEN CARE OF BY MORE
22       INTENSIVE AND/OR A DIFFERENT ';YPE OF SAMPLE CLEANUP,
23       MRI DOES HAVE ON ITS PHASE  II  AGENDA TO INVESTIGATE
24       TWO OTHER INDUSTRIES UNDER THEIR CONTRACT, WHICH IS
25       SUPERVISED BY PROJECT OFFICER STEVE BlLLETS OF EMSL

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 i       IN CINCINNATI,  ALSO,  I MUST MENTION THAT  THE  PROTOCOL
 2       WHICH YOU ARE GOING TO SECURE AT THE FRONT OF  THE
 3       ROOM, IF YOU PROMISE ME YOU'LL ONLY TAKE ONE,  DOES
 4       HAVE CHANGES AND REVISIONS  IN IT, AND THE COVER
 5       PAGE REALLY IS NOT ACCURATE,  A LOT OF THIS
 6       REVISION WORK AND THE METALS METHODS WHICH ARE
 7       ATTACHED AND THE CAPILLARY  METHODS WHICH ARE ATTACHED
 8       WERE DONE UNDER DR. EARL HANSEN,EVEN THOUGH CLARENCE
 9       HAILE WAS THE PERSON WHO WAS INVOLVED  IN THE ORIGINAL
10       RESEARCH,
n         NOW,  I WILL TRY TO PROCEED WITH THE  PROTOCOL.
12       FOR THE PURGEABLE ORGANICS, THE METHOD OF  BELLAR AND
13       LlCHTENBERG IS BASICALLY UTILIZED WITH SOME
14       REVISIONS,  THE SAMPLE OF SLUDGE is DILUTED TO
15       ,5 PERCENT TOTAL SOLIDS FOR  CONFORMITY'S SAKE,  IT'S
        NECESSARY TO RUN PERCENT SOLIDS DETERMINATIONS ON
ID
17       EACH SAMPLE,  THIS  INFORMATION WILL ALSO BE NECESSARY
18       IF ANYONE DOES WANT THE RESULTS ON A DRY WEIGHT BASIS,
19       AS A SIDELINE, THE  POTW VOA SAMPLE  IS  COMPOSITE OF
20       SIX 4-HOUR SAMPLES  MIXED AT THE  LABORATORY,  WE DO
21       NOT KNOW, AT THIS TIME, WHETHER OR NOT THE INDUSTRIAL
22       SAMPLES WILL HAVE TO BE COMPOSITED,  THE TEKMAP. LIQUID
23       SAMPLE CONCENTRATOR, LSC-1  OR  ITS EQUIVALENT  is USED
24       WITH SUITABLE MODIFICATIONS> SUCH AS,  THE  TRAP IS
25       PACKED  IN THE FOLLOWING ORDER!   GLASS  WOOL IN  THE
                                  293

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 1        INLET END, FOLLOWED BY OV-1, TENAX, SILICA GEL,
 2       CHARCOAL AND THEN AGAIN GLASS WOOL, WHICH DOES
 3       DIFFER FROM THE WASTEWATER REQUIREMENTS OF ONLY
 4       TENAX AND SILICA GEL,  THE TRAP MUST BE INSTALLED
 5       SO THAT THE PURGED EFFLUENT ENTERS THE TENAX END
 6       OF THE TRAP OR IT DOESN'T WORK RIGHT,  AFTER
 7       CONDITIONING THE TRAP, YOU TRANSFER THE PROPER
 8       AMOUNT OF SLUDGE TO CONTAIN 50 MILLIGRAMS OF DRY
 9       SOLIDS WITH A PIPETTE WITH THE TIP CUT OFF, THEN
10       YOU BRING YOUR LEVEL UP TO 10 MILLILITERS WITH
11       YOUR ORGANIC-FREE WATER AND ADD YOUR METHOD
12       RECOVERY SPIKES, THEN YOU PROCEED WITH YOUR PURGE
13       AND TRAP IN THE USUAL WAY, BACKFLUSHING INTO
14       THE GC WITH THE PROPER PROGRAMMING, WHICH IS ALL
15       IN THE PROTOCOL AND WHICH I'M SURE YOU ALL PROBABLY
16       KNOW ALREADY INSIDE OUT,   YOU HOLD THIS PROGRAMMING
17       UNTIL COMPLETE COMPOUND ELUTION HAS OCCURRED
18       AND THEN THE PURGING DEVICE MUST BE CLEANED OR
19       CHANGED BETWEEN SAMPLES BECAUSE SLUDGES, NEEDLESS
20       TO SAY, ARE GOING TO PROVIDE MUCH DIRTIER AND MANY
21       MORE PROBLEMS WITH DIRT THAN YOUR WASTEWATER
22       SAMPLES OR ANY KIND OF A CLEAN WATER SAMPLE.  THE
23       SAMPLE IS ANALYZED BY fiC/MS USING A COLUMN
24       PACKED WITH  ,2 PERCENT CARBOWAX, 1500 ON 80/100
25       MESH  CARBOPACK C,   THE  MASS  SPEC SHOULD  BE

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 1       REPETITIVELY  SCANNED  OVER  THE  RANGE,  M/E,  20 TO 275



 2       AT 3 TO 5 SECONDS PER  SCAN,   YOUR STANDARDS,  BLANKS,



 3       SAMPLE PRESERVATIONS AND QA/QC REQUIREMENTS ARE



 4       DESCRIBED IN  THE PROTOCOL.   NOW,  WE COME TO THE



 5       HARD PART,  THE  EXTRACTION  OF THE  SEMI VOLATILE



 6       ORGANICS,




 1         R)UR SAMPLES MAY BE PREPARED AT  A  TIME, IF ADEQUATE



 8       EQUIPMENT IS  AVAILABLE IN  YOUR LABORATORY FOR



 9       HOMOGENIZATION, CENTRIFUGATION, EXTRACTION,  AND



10       YOUR KD CONCENTRATION,  YOU  THOROUGHLY MIX THE



11       SLUDGE SAMPLES  BY HOMOGENIZING IN THE  SAMPLE  BOTTLE



12       USING A HIGH-CAPACITY  TlSSUEMIZER OR THE EQUIVALENT,



13       YOU QUICKLY REMOVE  AN  80 MILLILITER ALIQUOT INTO  A



14       1QO-MILLILITER  GRADUATE, TRANSFER THE  ALIQUOT INTO



15       A 250-MILLILITER CENTRIFUGE  TUBE,



16          YOU BASIFY EACH  ALIQUOT EQUAL  TO OR GREATER



17       THAN PH 11  WITH SODIUM HYDROXIDE  AND MIX BRIEFLY



18       WITH THE HOMOGENIZER TO  HAVE A UNIFORM PH, OR



19       AS  CLOSE TO  A UNIFORM  PH  AS ONE  CAN  GET




20       WITH SLUDGE,    YOU  ADD 80  MILLILITERS  OF METHYLENE



21       CHLORIDE TO EACH SAMPLE  AND  HOMOGENIZE AGAIN



22       BRIEFLY SO  YOU  DON'T HAVE  ANY HEAT  FROM  FRICTION,



23       AND YOU CENTRIFUGE  AT  3,000  RPfl'S FOR 30  MINUTES,



24       YOU WITHDRAW  YOUR EXTRACT  FROM THE  CENTRIFUGE



25       TUBE BY  INSERTING A 100-MILLILITER  PIPETTE INTO THE
                                   295

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1       SOLIDS CAKE AT THE WATER-METHYLENE CHLORIDE  INTERFACE
2       AND THEN YOU DISCHARGE THE EXTRACT INTO  A  500-MILLILITER
3       SEPARATORY FUNNEL,  YOU REPEAT THE EXTRACTION  TWICE
4       MORE, YOU DRY IT, AND K-D THE COMBINED EXTRACTS  AFTER
5       WASHING THE DRYING COLUMN AND FOLLOWING  YOUR USUAL
6       PROCEDURES AND YOU THEN TRANSFER YOUR EXTRACT  TO A
7       VOLUMETRIC AND YOU STORE AT 4 DEGREES FOR  GPC  CLEANUP,
8         THE GPC CLEANUP is PROBABLY ONE OF THE MOST
9       SIGNIFICANT ADDITIONS TO THE METHOD, VARYING FROM
10       YOUR PROTOCOL FOR YOUR OTHER 304H METHODS,   FOR  THE
11       GEL PERMEATION CHROMATOGRAPHY CLEANUP,, A GPC AUTO PREP
12       1002, MADE BY ANALYTICAL BIOCHEMISTRY LABS,  INCORPORATED,
13       OR ITS EQUIVALENT,, WHICH WOULD BE A BANK  OF COLUMNS
14       SET UP FOR GPC WITH BlO BEADS SX~3, AND THIS  HAS  TO BE
15       PROPERLY CALIBRATED AS DESCRIBED IN THE  PROTOCOL.
16       THE SAMPLE EXTRACTS ARE PROCESSED USING  THE  DUMP;
17       COLLECT  AND WASH PARAMETERS WHICH YOU ESTABLISHED  IN
18       YOUR CALIBRATION, AND THE CALIBRATION, OBVIOUSLY,
19       HAS TO BE RIGHT  OR YOU'RE GOING TO LOSE  SOME OF
20       YOUR IMPORTANT ANALYTES  IN THESE FRACTIONS,  THE
21       CLEANED EXTRACTS ARE ALSO CONCENTRATED AND STORED
22       FOR YOUR GC/flS ANALYSES,
23         THE BASE/NEUTRAL/PESTICIDE EXTRACT  IS ANALYZED
24       BY GC/MS USING THE 3 PERCENT SP-2250 ON  100/120
25       MESH SUPELCOPORT UNDER THE APPROPRIATE
                                  -116.

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1

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3

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5

6

7

8

9

10

11

12

13

14

15

16
17

18

19

20

21

22

23

24

25
CONDITIONS, THE MS SHOULD BE REPETITIVELY  SCANNED
OVER THE RANGE M/E ^0 TO 475 AT THREE SECONDS PER
SCAN AND THE EXTRACT SHOULD BE SPIKED WITH 50
MICROLITERS OF THE DJQ  ANTHRACENE, INTERNAL
STANDARD,  THE DATA HANDLING STANDARD AND BLANK
INFORMATION AND QA/QC REQUIREMENTS, AGAIN, ARE
IN THE PROTOCOL.
  ANOTHER SIGNIFICANT CHANGE is THAT WE ARE
CONSIDERING THE ADDITION OF CAPILLARY METHODS,
WE HAVE  PURSUED THE POSSIBILITY OF USING
CAPILLARY COLUMN GC/MS FOR GETTING BETTER
INFORMATION ABOUT THE BASE/NEUTRAL AND PESTICIDE
FRACTION,  SEVERAL BASE/NEUTRAL EXTRACTS WERE
SHOT PRIOR TO AND AFTER  FLOROCIL CLEANUP,  THE
AVAILABLE  INFORMATION DOES NOT INDICATE THAT
THERE WILL BE MUCH BETTER RESOLUTION IN PACKED
COLUMNS,   I THINK THIS SHOWS US THAT MRI DOES
REALLY GOOD WORK WITH PACKED COLUMNS,   HOWEVER, IN
INSTANCES OF VERY DIFFICULT SAMPLES, SUCH AS 7.IMPRO
SLUDGES, THE CAP METHOD MAY BE USEFUL,  IT WILL
BE USING AN SE-54CAPILLARY COLUMN, EVALUATED
BY PROPER TESTING SUCH AS THE GROB.STANDARDIZED
QUALITY  TESTS FOR CAPILLARY COLUMNS PUBLISHED
IN THE JOURNAL OF CHROMOTOGRAPHY, NUMBER 156,
                                _297_

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 i            THE GROB TEST OFFERS INFORMATION ABOUT THE
 2       ABSORPTION OF THE HYDROXYL FUNCTION AND THE
 3       ALDEHYDE FUNCTION, SEPARATION EFFICIENCY, ACID
 4       BASE BEHAVIOR, FILM THICKNESS, AND IT DOES THIS
 5       USING A SINGLE MIXTURE.  HOWEVER, I BELIEVE MORE
 6       STRINGENT TESTS ARE GOING TO BE NECESSARY THAN THE
 7       GROB TESTS,  WE ARE GETTING INFORMATION THAT MANY,
 8       MANY CAPILLARY COLUMNS ARE PASSING THE GROB TEST AND
 9       STILL WE ARE LOSING SOME VERY IMPORTANT BAD ACTORS
10       IN THE BASE/NEUTRAL FRACTION, AND I AM IN THE PROCESS
11       OF GETTING SOME INFORMATION ON NEW MIXTURES THAT ARE
12       BEING MADE UP TO MAKE MUCH MORE APPROPRIATE TESTS,
13       AND WHEN THIS IS ALL PUT TOGETHER, ANYBODY WHO WANTS
14       THE INFORMATION WILL BE ABLE TO HAVE IT,
15            THE FLOROCIL CLEANUP WAS EXAMINED FOR THE
16       EXTRACTS TESTED, BUT IT DID SHOW A SIGNIFICANT LOSS
17       OF ANALYTE IN MOST CASES, THOUGH A CLEANER BACKGROUND
18       DID EXIST,
19            SHORTCOMINGS:  THESE ORGANIC PRIORITY
20       POLLUTANT  ANALYSES IN SLUDGE SUFFER BASICALLY
21       THE SAME AS THOSE OF THE WASTEWATER SAMPLES,
22       SUCH AS THE DETECTION OF BENZIDENE AND SOME
23       OF  YOUR  OTHER  TROUBLEMAKERS,   HOWEVER,   I  DO
24       NOT BELIEVE THESE ARE A PROBLEM WITH THE METHOD-
25       OLOGY BUT  IN THE POOR CHROMATOGRAPHY OF THESE
                                  298

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 1       TYPES OF  CONSTITUENTS.
 2            NOW.,  I'M  GOING  TO  COME  TO  OUR  METALS
 3       ANALYSES,   I'LL  POINT OUT  THAT  THE  PROTOCOL
 4       FOR THE METALS THAT  IS  ATTACHED IS  NOT
 5       REALLY WRITTEN UP  AS A PROTOCOL,   IT'S  SORT
 6       OF A SKETCHY DESCRIPTION OF  WHAT IS BEING  DONE, AND
 7       EVENTUALLY  IT  WILL BE WRITTEN UP AS A PROTOCOL,OR
 8       SOMETHING WILL,  MRI HAS BEEN UTILIZING  FOUR
 9       DIGESTIONS  FOR THE ANALYSIS  OF  THE  13 PRIORITY
10       POLLUTANTS.  FOR BERYLLIUM, CADMIUM,  CHROMIUM, COPPER,
11       NICKEL, SILVER,  THALLIUM,  AND ZINC,  THEY'RE USING
12       AN ALIQUOT OF  SLUDGE UNDERGOING A PRELIMINARY
13       OXIDATION BY REFLUXING  WITH  NITRIC  AND SULFURIC  ACID
14       UNTIL YOUR  OXIDES OF NITROGEN  FUMES ARE GONE, THE
15       SOLUTION  CLARIFIES AND  THE SOLIDS LIGHTEN IN COLOR,
16       THE SAMPLE  IS  COOLED AND NITRIC AND PERCHLORIC
17       ACID,WHICH  is  EVERYBODY'S  FAVORITE,ARE ADDED AND
18       THE SAMPLE  IS  HEATED TO THE  OXIDIZING STAGE OF THE
19       PERCHLORIC  ACID,   AFTER THE  REMAINING ORGANIC
20       MATERIAL  IS DESTROYED,  THE SAMPLE IS TRANSFERRED
21       WITH DI WATER  TO A SMALL BEAKER, THE REMAINING
22       PERCHLORIC  ACID  FUMED OFF  AND THE SULFURIC ACID
23       REMAINS,  THE SAMPLE  IS  DILUTED  AND  ANALYZED BY
24        FLAME ATOMIC ABSORPTION, ANY SAMPLE  THAT IS  DETECTED AT
25

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 1       LESS THAN 20 MICROGRAMS PER KILOGRAM, WE ARE



 2       GOING TO REQUEST TO BE REANALYZED BY FLAMELESS AA,



 3       WE EXPECT THE MOST LIKELY CANDIDATES WILL BE



 4       BERYLLIUM AND THALLIUM,



 5            THE SECOND DIGESTION FOR ARSENIC, ANTIMONY AND



 6       SELENIUM:  AN ALIQUOT  IS REFLUXED FOR APPROXIMATELY



 7       8 HOURS—IT SOUNDS LIKE A LONG TIME—WITH NITRIC



 8       ACID AND SULFURIC; IT  IS COOLED AND ALIQUOTS OF



 9       30 PERCENT HYDROGEN PEROXIDE ARE ADDED,  THE



10       SAMPLE  IS EVAPORATED,  REFLUXED FOR ABOUT TWO HOURS



11       WITH A  MIXTURE OF NITRIC AND HYDROCHLORIC AND



12       DILUTED,  GASEOUS HYDRIDE GENERATION WILL BE USED



13       FOR ANALYSIS,



14            THE THIRD DIGESTION IS FOR LEAD, AND THE MAIN



15       REASON  BEING WE CANNOT PULL IT OUT OF THE FIRST



16       DIGESTION BECAUSE OF THE SULFURIC ACID.  AN



17       ALIQUOT IS DRYED AND ASHED FOR 8 HOURS,  THE



1«       SAMPLE  IS REFLUXED FOR 2 HOURS WITH NITRIC ACID



19       AND COOLED,  MORE NITRIC IS ADDED AND EVAPORATED,



20       THE SAMPLE IS CENTRIFUGED AND RINSED,  THE RINSES



21       ARE EVAPORATED AND DILUTED WITH 10 MILLILITERS



22       OF NITRIC ACID,  FLAME AA WILL BE USED FOR ANALYSIS,



23       AND FLAMELESS IF ABSOLUTELY NECESSARY, WHICH WILL



24       BE HIGHLY UNLIKELY,




26             OUR  LAST METAL,  BUT CERTAINLY  NOT LEAST,
                                 300

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1        IS  MERCURY,   AN ALIQUOT OF SAMPLE IS CENTRIFUGED
2        AND THE  SUPERNATANT DECANTED AND TREATED AS A
3        SEPARATE SAMPLE.   THE SUPERNATANT IS REFLUXED FOR
4       16  HOURS WITH NITRIC ACID AND SULFURIC ACID IN AN
5       OIL BATH MAINTAINED AT 60 DEGREES,   IT IS THEN
6       REACTED  FOR  ABOUT 4 HOURS WITH 6 PERCENT POTASSIUM
7       PERMANGANATE,
«        THE EXCESS PERMANGANATE IS REMOVED BY DROPWISE
9       ADDITION OF  SALT/HYDROXLAMINE HYDROCHLORIDE
10       SOLUTION,  THE CENTRIFUGE SOLID is  TRANSFERRED TO
11       A BEAKER BY  RINSING WITH NITRIC ACID,   THE
12       RINSE SAMPLE IS REFLUXED FOR  30, BELIEVE IT OR
13       NOT,  HOURS OR UNTIL THE SAMPLE IS DECOLORIZED,
14       WE'RE HOPING IT WON'T REALLY TAKE 80 HOURS, BUT
15       THEY EVIDENTLY DO SOMETIMES,  IT IS REFLUXED
16       WITH SULFURIC ACID AND COOLED AND AGAIN REACTED
17       WITH PERMANGANATE, WHICH THE EXCESS IS REMOVED
18       WITH THE HYDROXLAMINE HYDROCHLORIDE.   THE
19       SOLID AND LIQUID FACTIONS ARE ANALYZED SEPARATELY
20       FOR MERCURY  BY THE COLD VAPOR TECHNIQUE,
21         I MIGHT NOTE HERE THAT ALL THE DATA SO FAR
22       SHOWS THAT THE MERCURY HAS ADSORBED COMPLETELY
23       INTO THE SOLID PHASE,  THIS HAS BEEN FOUND TO BE
24       TRUE EVEN WITH THE SPIKES,  HOWEVER,  THE AQUEOUS
25       PHASE MUST ALSO BE ANALYZED, AS WE CAN'T REALLY BE
                                301

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                                                           9
1        POSITIVE THAT THIS WILL ALWAYS BE TRUE,   POOR
2       RECOVERY DATA WAS OBTAINED WHEN THOSE PHASES
3       WERE NOT SEPARATED,  As YOU CAN GUESS, THE MAIN
4       PROBLEMS ASSOCIATED WITH THESE METHODS ARE THE
5       ENORMOUS TIMES UTILIZED FOR DIGESTIONS AND THE NUMBER
6       OF DIGESTIONS, AND I THINK YOU'RE GOING TO HAVE TO
1       USE AN AWFUL LOT OF GLASSWARE.
s         WE'RE PRESENTLY DISCUSSING, ONLY DISCUSSING,
9       POSSIBILITIES FOR REDUCING THE NUMBER OF DIGESTIONS
10       SUCH AS PULLING ARSENIC, SELENIUM, AND ANTIMONY OUT
11       OF THE FIRST DIGESTION BY REMOVING THE OXIDES OF
12       NITROGEN,WHICH WOULD BE A HINDRANCE TO HYDRIDE
13       GENERATION,  WE COULD ALSO POSSIBLY GET LEAD OUT
14       OF THE FIRST DIGESTION BY DISSOLVING THE LEAD IN
15       AMMONIUM ACETATE LIKE YOU WOULD DO IN YOUR DITHIZONE
16       METHOD FOR COLORIMETRIC ANALYSIS,
i?         SOMEBODY ELSE DID SUGGEST A POSSIBILITY TO ME
18       OF USING THE MERCURY DIGESTION FOR ARSENIC, SELENIUM
19       AND ANTIMONY AS LONG AS THE EXCESS PERMANGANATE
20       IS ADEQUATELY REMOVED,   THIS WOULD BE VERY IMPORTANT
21       SINCE YOU'RE DOING A REDUCTION WITH STANNOUS
22       CHLORIDE AND YOU MIGHT HAVE A LITTLE PROBLEM WITH
23       THE PERMANGANATE  AND THE STANNOUS CHLORIDE
2«       HAVING A BATTLE,
25         ANOTHER PROBLEM WITH THE METHOD is THE USE OF
                                 302

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                                                           13
 1        PERCHLORIC  ACID,   SOME  PEOPLE ARE AFRAID OF IT,   II
 2        IS  CONSIDERED  UNDESIRABLE  BECAUSE OF THE DANGER
 3        OF  EXPLOSION WHEN  IN  CONTACT WITH ORGANIC MATTER,
 4        A SPECIAL  PERCHLORIC  ACID HOOD IS  DEFINITELY AN
 5        ASSET,   THE USE  OF SULFURIC ACID  IN THE DIGESTION
 6        IS  A  SAFETY FACTOR, BUT SOMETIMES PEOPLE ARE STILL
 7        AFRAID  OF  IT,  WE'VE  ALSO  CONSIDERED THE USE OF  A
 8        METHOD  DEVELOPED BY EHSL,  CINCINNATI, ENTITLED
 9        INTERIM METHOD FOR THE  ANALYSIS OF ELEMENTAL
10        PRIORITY POLLUTANTS  IN  SLUDGE,  DATED DECEMBER
11        1978,AND I  KEEP  HOPING  THAT THIS  'INTERIM'METHOD
12        WILL  BECOME SOMETHING BEYOND THE  'INTERIM*  METHOD  AND
13        BECOME  A'FINAL'METHOD,   THE PROTOCOL DEMANDS
14        THE SEDIMENT METHOD FOR COLD VAPOR ANALYSIS OF
15        MERCURY, WHICH  IS RIGHT  IN  YOUR EPA METHODS  FOR
16        CHEMICAL ANALYSIS  OF  WATER AND WASTE.
17         THE OTHER PRIORITY  POLLUTANT METALS ARE ANALYZED
18        FROM  A  SINGLE  DIGESTI ON, AND THE SAMPLE IS DRIED,
19        PULVERIZED  AND MIXEDJ NITRIC ACID IS ADDED,AND THE
20        SAMPLE  IS  REFLUXED TO NEAR DRYNESS,   THE SAMPLE
21        IS  COOLEDj  NITRIC  ACID  IS  ADDED AGAIN AND REFLUXED
22        AGAIN ALMOST TO  DRYNESSj  COOLED AGAIN AND MORE
23        NITRIC  IS  ADDED, AND THEN 3 PERCENT HYDROGEN
24        PEROXIDE,   YOU RETURN THE  BEAKER  TO A HOT PLATE
25        AND YOU WARM TO  START THE  PEROXIDE REACTION, THEN
                                 303

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1        YOU HEAT UNTIL THE CESSATION OF EFFERVESCENCE.
2       DEPENDING ON THE METHOD OF ANALYSIS OR PARAMETER
3       TO BE DETERMINED, FURTHER REFLUX AND FILTRATION
4       WILL BE NECESSARY AND ALSO THE ADDITION OF MATRIX
5       MODIFIERS IN SOME CASES,
e         UNFORTUNATELY WE HAVE LITTLE OR NO DATA ON
7       THIS ALL-ENCOMPASSING DIGESTION,  IT SOUNDS VERY
8       IDEAL, BUT UNTIL WE GET SOME KIND OF DATA TELLING
9       US HOW IDEAL IT IS, WE REALLY CAN'T DO TOO
10       MUCH WITH IT,
11         NOW, FOR THE PIECE DE RESISTANCE,  FOR OUR
12      VISITING  CAPITALISTS, THE PEOPLE WHO ARE INTERESTED
13       IN HOW THEY CAN MAKE SOME MONEY AROUND HERE,
14       AN IFB IS PRESENTLY IN THE CONTRACTS OFFICE AND WILL
15       HOPEFULLY BE ON THE STREET BY MARCH OR APRIL
16       FOR THE ANALYSIS OF POTW AND INDUSTRIAL SLUDGES
17       UTILIZING THESE METHODS, IN ADDITION, THE
18       TRADITIONAL PARAMETERS OF TOC, COD, AND TOTAL
19       SUSPENDED SOLIDS WILL BE REQUIRED,  SOME PEOPLE
20       MAY WANT TO KNOW WHY WE CHOSE  TOC, AND THE MAIN
21       REASON IS IT'S THE LESSER OF TWO EVILS BETWEEN
22       TOCs AND BODsj THAT'S REALLY ABOUT THE BEST
23       REASON I CAN GIVE.  THE IFB  WILL CONSIST OF
24       1,000 SAMPLES, 5 BID LOTS OF 200 SAMPLES EACH,
25       THE LAB MUST BE CAPABLE OF PROCESSING 20 SAMPLES
                                 304

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        PER MONTH, YOU MUST KEEP  IN MIND THAT THE  METALS
        WILL INVOLVE ABOUT 3,000  ANALYSES; WHICH, IF YOU
3       FIGURE IT OUT, IS 200 SAMPLES TIMES 13 METALS,  PLUS
4       SOME BEING DONE BY FLAMELESS, THAT'S ABOUT THE
5       BEST NUMBER WE COULD COME UP WITH,  WE  DECIDED
6       ON COMBINING THE INORGANIC ANALYSES IN  THIS  IFB
7       PARTLY BECAUSE I THINK  IT MIGHT BE VERY  HELPFUL
        IN  BALANCING  THE  WORKLOAD OF A  LABORATORY,
9       AND WE CHOSE AA FOR THIS  BECAUSE WE ARE  SOMEWHAT
10       LIMITED WITH ICAP BECAUSE EVERYBODY DOESN'T  HAVE
        ONE,   I THINK ALMOST EVERYBODY HAS AN AA,
12         I WOULD LIKE TO INVITE  TO THE PODIUM  AT  THIS
13       TIME EARL HANSEN FROM MIDWEST RESEARCH  INSTITUTE,
14       EARL is GOING TO HELP ME  FIELD ANY QUESTIONS
15       REF, THE PROTOCOL,AND WE  MAY CALL UPON  JlM
16       LONGBOTTOM, ALSO, SINCE HE  WAS INVOLVED IN THE
17       ORIGINAL CONTRACT,  HE  MAY HAVE TO ANSWER  SOME
18       OF OUR QUESTIONS,  IF HE WOULD LIKE TO COME UP,
19       $0  IF  YOU HAVE ANY QUESTIONS ON PROTOCOL,  THEY
20       SHOULD BE DIRECTED PROBABLY TO EARL AND IF
21       IT'S ANYTHING ABOUT THE IFB, THEY SHOULD BE
22       DIRECTED TO ME.
23
24
25
                                305

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 1
 2                                DR. HANSEN:  I'D LIKE TO MAKE
 3       ONE COMMENT WITH REGARD TO THE METALS ANALYSIS. I'M
 4       SURE THAT SOME PEOPLE WHO ARE FAMILIAR WITH THAT PORTION
 5       OF THE ANALYTICAL LOAD MIGHT BE A LITTLE SHELLSHOCKED
 6       AT THE AMOUNT OF TIME IT APPEARS IT TAKES TO GET
 7       THOSE ANALYSES DONE.
 8         TO QUOTE A PHRASE OF BILL'S, WE'VE BEEN EXAMINING
 9       WHY WE'RE IN THE SWAMP SINCE ABOUT SEPTEMBER ON A
10       SUPPORT OF A SURVEY PROGRAM FOR EPA, POTW SLUDGE
11       ANALYSIS.  SO MUCH OF THE METHODS DEVELOPMENT WHICH
12       WAS DONE FOR THE METALS ANALYSIS WAS DONE PREVIOUS
13       TO OUR BEGINNING THIS PROJECT AND SO WE REALLY
14       HAVEN'T HAD MUCH TIME TO OPTIMIZE THE METALS
15       ANALYSIS METHODS AND  I'D SUGGEST THAT THERE  IS
16       PROBABLY A SUBSTANTIAL AMOUNT OF METHODS OPTIMIZATION
17       WHICH CAN BE DONE WITH REGARD TO THE METALS.
is                                MR, MOBERG:  BUD MOBERG,
19        ARLI.  THERE WERE SOME DIFFERENCES BETWEEN  THIS METHOD
20       SO FAR AS THE GLASS COLUMN, EIGHTH-INCH COLUMN,
21       AND THE PROTOCOL.  FOR EXAMPLE,  IT WAS SUGGESTED THE
22         2250DB HAD BEEN USED AND HERE YOU OMITTED THE  DB
23       TREATMENT; AT LEAST  IT DOESN'T SHOW  IT  IN THE  WRITING,
24                                DR, HANSEN:  WE'RE  NOT
25       USING DB,

-------
                                                             17
 1                                MR, MOBERG:  YOU'RE  NOT
 2       USING THE DB,  CAN YOU GIVE ANY  REASON  FOR THAT?
 3                                DR, HANSEN:  YOU'VE  GOT  TO
 4       GET THE HISTORICAL APPLICATION ON THAT  DEVELOPMENT
 5       PROGRAM WHICH  IS OUTLINED, OR AT LEAST  YOUR HISTORY,
 6       DO YOU HAVE A  COMMENT ON THAT, JlM?
 i                                MR, LONGBOTTOM: WHAT'S THE
 8       QUESTION, I'M  SORRY,
 9                                MR, MOBERG:  THIS METHOD
10       DOES NOT SHOW  2250DB, BUT JUST THE 2250 PACKING MATERIAL,
11                                MR, LONGBOTTOM:  YES,
12                                MR, MOBERG:  THERE is AN
13       IMPROVEMENT OF THE DB MATERIAL OVER THE 2250  STRAIGHT,
14       Is THERE ANY REASON  FOR BACKTRACKING?
15                                MR, LONGBOTTOM:  I DON'T
16       THINK ON THE WHOLE THE DB REALLY WORKED OUT THAT WELL.
17       THERE WERE PEOPLE THAT WEREN'T HAPPY WITH THE
18       SEPARATIONS, FOR ONE  THING, AND JUST BY CONSENSUS
19       WE'VE JUST MIGRATED  BACK TO THE  2250 AND ELIMINATED
20       THE BASE DEACTIVATION,
21                                MR, MOBERG:  I SEE.
22                                DR, NEPTUNE:   DEAN NEPTUNE,
23       EPA,  I THINK  I CAN  SPEAK TO THAT A LITTLE BIT MORE
24       CLEARLY,  YES, WE DID GET SOME 2250DB MATERIAL WHICH
25       WAS VERY ADEQUATE AND  IN MANY CASES SUPERIOR  TO THE
                                307

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1        2250 FOR PROVIDING SEPARATIONS,  THE PRIMARY REASON
2       WHY WE HAVE NOT CONTINUED TO USE THE DB WAS
3       BECAUSE OF THE RELATIVELY SHORT COLUMN LIFE
4       THAT ONE HAS WITH USING THE DB,  IF YOU'LL
5       REMEMBER, MOST OF THE MATERIALS THAT WE WERE
6       FINDING YOU'D GET LIKE 25 RUNS AND THAT MIGHT BE
7       A GOOD COLUMN, ASSUMING THAT YOUR SAMPLES WERE
8       NOT EXTREMELY CRUDDY AND IT WAS THE CONSENSUS
9       OF EVERYBODY THAT THE ADVANTAGE GAINED FROM THE
10       DB WAS NOT LARGE ENOUGH TO MAKE UP FOR THE
11       DISADVANTAGE OF THE VERY SHORT COLUMN LIFE,
12                                MR, MOBERG:  I WAS
13       CONCERNED WITH THE BENZIDINE PRINCIPALLY BECAUSE
14       IT WAS SO MUCH BETTER WITH THE DB,
15                                DR, NEPTUNE:  THAT'S EXACTLY
16       RIGHT,
17                                MR, MOBERG:  BUT WE STILL
18       HAD THE SAME LIMITATIONS ON BENZIDINE WITHOUT THE
is       DB,  I GUESS THAT'S THE IMPLICATION,
20                                DR, NEPTUNE:  YES, THAT'S
21       CORRECT, AND AS I WAS POINTING OUT, THERE WERE, IN SOME
22       CASES, AN ADDED ADVANTAGE AND THAT'S ONE VERY GOOD
23       EXAMPLE OF WHAT YOU'RE TALKING ABOUT, OF USING THE
24       DB; BUT THE OTHER DISADVANTAGES OF THE EXTREMELY
25       SHORT COLUMN LIFE FAR OUTWEIGHED THE ADVANTAGES FROM

-------
1        TRYING  TO  USE  IT,
2                                MR,  MOBERG:   I  SEE.   ANOTHER
3       QUESTION OR  TWO.  YOU HAVE SUGGESTED A SCAN TIME
4       OF 3  SECONDS RATHER THAN 3 TO 5, AND IF YOU JUST SAY
5       3, I  THINK THAT  YOU CAN LOAD  UP YOUR DISKS A  LOT
6       FASTER  AND WE  HAVE  A SLIGHT PROBLEM THERE OF  CHANGING
7       ALL OF  OUR PROGRAMS AND THEN  MAKING COMPARISONS
8       BETWEEN THIS PROGRAM AND THE  SCREENING PROGRAM AS
9       WELL.   NO  COMMENT?
10                                DR.  HANSEd:  ARE YOU
11       TALKING ABOUT  METHODS 624 AND 625?
12                                MR,  MOBERG:   IN HERE, THE
13       SCAN  TIME  AND  THE TEMPERATURE PROGRAMMING THAT WAS
14       INCREASED  10 DEGREES A MINUTE SO THAT NOW YOU'RE
15       GOING TO CHANGE  ALL OF YOUR RELATIVE RETENTION, I
16       MEAN  YOUR  RETENTION TIMES RATHER DRAMATICALLY AT
17       LEAST IN THE EARLY  PART OF THE CHROMATOGRAM,
18                                B3,  HANSEN:.  I  BELIEVE THAT
19       QUESTION SHOULD  BE  DIRECTED.,,
20                                MR,  MOBERG:   WELL,  IT'S TO
21       MRI OR  TO  EPA  OR WHOEVER WANTS TO HANDLE IT,
22                                DR,  HANSEri:   WE'VE BEEN
23       UTILIZING  THIS PROTOCOL AS WRITTEN ON THE SURVEY PROGRAM,
24       AND WE'VE  COMPLETED PROBABLY  SEVEN PLANTS'WORTH OF POTW
25       SLUDGES,   So I CAN'T RESPOND  TO THE HISTORICAL PART OF
                                 309

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 1       YOUR QUESTION WITH REGARD TO HOW BOTH CONDITIONS
 2       WERE ARRIVED AT,  BUT WE HAVE BEEN USING THOSE
 3       CONDITIONS,
 4                                MR, MOBERG:   MANY OF THE
 5       SCREENING LABORATORIES HAVE BEEN USING SLIGHTLY SLOWER
 6       RATES,
 7                                DR, HANSEN:   THAT'S NOT
 8       RELATED TO THE DATA BASE AT THIS TIME, WE'RE JUST
 9       DOING THE ANALYSIS,
10                                MR, MOBERG:   EXCEPT THAT THIS
11       IS THE WAY AN IFB WILL COME OUT AND IF YOU'RE GOING TO
12       RESPOND AND YOU HAVE WORK FROM BOTH CASES NOW, YOU
13       HAVE PARAMETERS THAT ARE DIFFERENT AND IT DOES MAKE IT
14       A LITTLE HEAVY TO KEEP CHANGING PARAMETERS,
is                                MS, FISK:   THAT'S A GOOD
16       POINT,
17                                J)R, HAHSEN:  THAT'S A HEAVY,
18       REALLY,
19                                MS, FISK:   You CAN'T EXPECT
20       US TO PICK UP ALL THE PROBLEMS ALL AT ONE TIME,
21                                MR, TELLIARD:  THE NEXT
22       QUESTION,
23                                MR, FISHER:   JOAN, BOB FISHER
24       WITH THE NATIONAL COUNCIL OF THE PAPER INDUSTRY,  As
25       YOU KNOW, THERE IS ALSO CONSIDERABLE EFFORT ONGOING
                                .310.

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 1       AMONG  EPA  AND  ITS  CONTRACTORS  DESIGNED TOWARD
 2       DEVELOPING METHODS FOR  THE  GENERATION  OF AND
 3       THE ANALYSIS OF  AN ARTIFICIAL  LEACHATE
 4       FROM SLUDGES,    DOES  YOUR WORK INTERFACE WITH
 5       THAT WORK  AT ALL?    IN  OTHER WORDS,  YOU'RE
 6       LOOKING AT,  IF I UNDERSTAND CORRECTLY, ESSENTIALLY
 7       TOTAL  PRIORITY POLLUTANTS  IN A SLUDGE.
 8                                MR, TELLIARD;  YES,  WE
 9       ARE LOOKING AT THAT,
10                                MR, FISHER:   IN THIS
H       PROGRAM?
12                                MR, TELLIARD:  You  MEAN
13       DOES THIS  METHOD APPLY  TO A LEACHABILITY TEST,
14       IS THAT THE QUESTION?
15                                MR, FISHER;   Is YOUR
16       ACTIVITY ADDRESSING LEACHATE ANALYSES  AT ALL?
17       I MEAN, A  GENERATION  OF AN  ARTIFICIAL  LEACHATE
18       AND THE ANALYSIS OF THAT LEACHATE?
19                                MS, FISK :   WE ARE  NOT
20       ADDRESSING THE PROBLEM  OF LEACHATE  TESTING AT
2i       THIS POINT IF  YOU'RE  REFERRING TO SOIL ATTENUATION
22       OR MOBILITY STUDIES;  WE'RE  HOPING THAT SOME  OF
23       THE METHODS THAT WE'RE  DEVELOPING WILL BE USEFUL
24       IN FINDING OUT WHAT IS  IN THESE SOLID  WASTES,
25       SO THAT WHEN THEY'RE  CONCERNED WITH THEM LEACHING,
                                 311

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1       WE CAN HAVE SOME INFORMATION AS TO WHAT  STARTED
2       OUT IN THERE,
3                                DR, NEPTUNE:  BOB,  IN
4       REGARDS TO YOUR QUESTION,..
5                                MS, FISK:   YES,  I  WAS
6       JUST GOING TO SAY PERHAPS DEAN NEPTUNE MIGHT,,,
7                                DR, NEPTUNE:   ,.,TOTAL
8       CONTENT,
9                                MR, TELLIARD:   TOTAL CONTENT,
10                                MS, FISK:   NOT LEACHING,
n                                MR, FISHER:  Do YOU INTEND
12       TO LEAVE YOUR WORK THERE, AT TOTAL?
13                                MR, TELLIARD:   RIGHT NOW,
14       I MEAN, WE DO, US; BUT THAT DOESN'T  MEAN THAT OTHER
15       OFFICES HAVEN'T GOT OTHER NEEDS,
16                                MR, LICHTENBERG:   JIM LICHTENBEI^
17       EPA,  JUST A POINT OF CLARIFICATION  ON ARE YOU GOING
18       TO LEAVE THE WORK THERE,1 NO, WE ARE  APPROACHING THAT
19       PROBLEM IN-HOUSE IN OUR RESEARCH WORK IN  CINCINNATI  OF
20       THE LEACHATE PROBLEM AND A  SEDIMENT  PROBLEM IN GENERAL.
21                                MR, TELLIARD:   OUR  NEXT SPEAKER
22       IS GOING TO DISCUSS AN OVERVIEW AMD  AN UPDATE ON A
23       PROGRAM WE STARTED ABOUT THIS TIME LAST  YEAR,  IT WAS NOT
24       QUITE THIS TIME, IT WAS A LITTLE  LATER,  ON THE SELF-
25       MONITORING PROGRAM FOR ASBESTOS ANALYSIS,  PRISCILLA  HOLTZCL/JW
        FROM EGD IS GOING TO KIND OF BRING YOU UP TO DATE,
   	               312

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                UPDATE  ON ASBESTOS  ANALYSIS  PROGRAM

 1                        SELF  MONITORING

                    BY:  PRISCILLA HOLTZCLAW

           As BILL MENTIONED,  WE BEGAN  THIS PROGRAM
 3
         APPROXIMATELY A YEAR  AGO,   OUR INTENTION  IS  TO
 4
         SCREEN THE  INDUSTRIES THAT WE  ARE  CURRENTLY

         INVOLVED WITH IN  EGD,   FOR SAMPLING AND ANALYSIS

         PURPOSES, ASBESTOS  HAS BEEN SINGLED OUT AS A UNIQUE

         PRIORITY POLLUTANT  BECAUSE OF  THE  DIFFERENCES IN  THE

         ANALYSIS TECHNIQUES,   To  GIVE  THOSE OF  YOU WHO ARE

         NOT  FAMILIAR  WITH IT  JUST A .QUICK  BACKGROUND;  THE

         WAY  WE ARE  APPROACHING IT IS THAT  WE ARE  USING

         ONE  PROGRAM TO OVERVIEW ALL THE  DIFFERENT

12        INDUSTRIES,   WE ARE USING A SELF-SAMPLING

13        TECHNIQUE IN  WHICH  WE CONTACT  THE  PLANT WITH THE

         308  LETTER, WE SEND THEM  A PREPARED SAMPLING KIT

         AND  A  DESCRIPTION OF  THE  POINTS  AT WHICH  WE

16        WANT WATERS TO BE TAKEN FOR ANALYSIS, AND WE SEND

         THEM THE NAME OF  THE  LABORATORY  TO FORWARD IT
18
         TO,

           WE ARE ANALYZING  ONE PLANT PER ACTIVE SUB-

         CATEGORY IN EGD AND WE HAVE DECIDED TO  LOOK  AT
O1
         THIS TIME FOR CHRYSOTILE  FIBERS  ONLY,   As OF

         RIGHT  NOW,  WE HAVE  BEEN WORKING  WITH 22 DIFFERENT

23        INDUSTRIAL  CATEGORIES AND HAVE TAKEN SAMPLES

24        IN 99  ACTIVE  SUBCATEGORIES,  THE DATA IS  BACK IN~
25
                                  313

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 1       HOUSE AT THIS POINT AND IT IS BEING DISSEMINATED



 2       TO THE VARIOUS PROJECT OFFICERS AND TO THOSE



 3       PARTICULAR FACILITIES THAT HAVE REQUESTED TO



 4       RECEIVE THE INFORMATION,  WE HAVE TAKEN



 5       APPROXIMATELY 450 SAMPLES; OUT OF THESE, 300



 6       HAVE BEEN ANALYZED,  THE REMAINING SAMPLES



 7       CONSIST OF RAW WATER SAMPLES;  IN OTHER WORDS



 8       THE INFLUENT TO THE PLANT,  THESE WERE PREPARED,



 9       THE GRIDS WERE PREPARED FOR ANALYSIS, BUT WERE



10       NOT ANALYZED UNTIL WE DETERMINED WHETHER THERE



11       WAS ASBESTOS IN THE EFFLUENT FROM THE PLANT,



12       WE'VE BEEN ANALYZING THAT DATAJ WE ARE NOW



13       GOING BACK AND REVIEWING,  DETERMINING WHICH RAW



14       WATERS NEED TO BE DONE AND  THAT DATA, AGAIN,



15       WILL BE FORWARDED TO THE PLANTS,



16         WE ARE EVALUATING THE DATA FROM AN ANALYTICAL



17       POINT OF VIEW ONLY,  IN OTHER  WORDS, WE ARE



18       SAYING THAT THE DATA IS ANALYTICALLY SIGNIFICANT



19       IF THE LEVEL OF CHRYSOTILE IS FIVE TIMES THE



20       DETECTION LIMIT,



21         IN ASBESTOS ANALYSIS, WHICH  IS AN ELECTRON



22       MICROSCOPE TECHNIQUE, THE DETECTION LIMIT IS



23       DETERMINED AS THAT LEVEL (CONCENTRATION)



24       THAT WOULD BE IN A LITER OF WATER IF YOU SAW ONE



25       FIBER DURING YOUR ANALYSIS.

-------
 1          LET  ME  STRESS,  THIS  IS  AN  ANALYTICAL SIGNIFICANCE,
 2       WE ARE NOT  AT  THIS  TIME ATTEMPTING TO MAKE ANY
 3       DETERMINATION  ON  THE BASIS OF HEALTH OR TREATABILITY
 4       STANDPOINTS,   BECAUSE  IT  IS  SCREENING,  WE ARE ONLY
 5       SAYING, YES, THERE  IS  A POSITIVE  INDICATION OF CHRYSOTILE
 6       OR NO, THERE IS NOT A  POSITIVE  INDICATION  OF  CHRYSOTILE,
 7       OF THE RAW  WASTE  IN THE FINAL EFFLUENT SAMPLES
 8       THAT WE HAVE EVALUATED TO DATE, ABOUT 60 PERCENT
 9       ARE SHOWING POSITIVE INDICATIONS  OF CHRYSOTILE,
10          WE ARE  EXPECTING  A NUMBER  OF  THESE TO FALL  OUT
11       WHEN WE GO  BACK AND REVIEW THE  RAW WATERS  TO  SEE
12       WHETHER THE MATERIAL IS SIMPLY  BEING PASSED THROUGH
13       THE PLANT,  IN SOME CASES, WE KNOW THAT THE CHRYSOTILE
14       IS BEING  PRODUCED AS A PRODUCT  OF THEIR MANUFACTURING
15       PROCEDURE.  IN OTHER CASES, IT APPEARS  THAT IT IS
16       MORE AN ARTIFACT  OF THE PLANT,  I,E,,  IT  IS  COMING
17       FROM FILTERS OR FROM ASBESTOS PIPE  THAT
18       IS BEING  DISINTEGRATED,
19         WHILE WE  ARE DOING THIS INITIAL EVALUATION  OF THE
20       DATA TO HELP THE  PROJECT  OFFICERS,  WE  ARE  ALSO
21       USING  WHAT  WE'RE  GETTING  BACK TO  EVALUATE  THE METHOD
22       ITSELF,   THE ONE  THAT  WE  ARE USING WAS  DEVELOPED
23       FOR DRINKING WATER  AND WE HAVE  RUN INTO SOME  PROBLEMS
24       TRYING TO ADAPT THIS TO THE  WASTEWATERS,  NAMELY,
25       THE HIGH  LEVELS OF  SOLIDS THAT  ARE INTERFERING,
                                 315

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3       FOR THIS EVALUATION PURPOSE, WE ARE SPLITTING SAMPLES
4       BETWEEN LABORATORIES,   WE ARE RECOUNTING
5       PREPARED GRIDS BY THE SAME  LABORATORY, WE ARE
6       SWITCHING GRIDS BETWEEN LABORATORIES TO HAVE
7       THEM COUNTED BY ANOTHER LABORATORY,  WE ARE
2       USING STANDARD SAMPLES TO ATTEMPT TO DETERMINE
9       SOME MEASURE OF PRECISION BETWEEN LABORATORIES,
10       AND WE ARE ENCOURAGING THE  DEVELOPMENT OF
11       METHODS BY OTHER PEOPLE TO  HELP US WITH THIS
12       PROBLEM,  WE ARE ALSO LOOKING FOR SOME WAY TO
13       DETERMINE THE ACCURACY OF ASBESTOS COUNTING BECAUSE THIS
14       IS ONE THING THAT WE HAVE NO INFORMATION ON AT THIS
1*       TIME,
16                   THAT'S JUST ABOUT THE UPDATE,   IN
17       OTHER WORDS, WE'RE IN THE MIDDLE OF THE PROJECT;
18       WE'RE SAYING, YES, WE ARE FINDING CHRYSOTILE
19       IN THE WASTEWATERSj NO, WE  CANNOT SAY AT THIS
20       TIME WHETHER FROM A REGULATION  STANDPOINT  IT  IS
21       SIGNIFICANT,  THIS IS A SCREENING EFFORT,   WE
22       ARE NOT TAKING THE NUMBERS  AND  PUTTING A
23       SIGNIFICANCE ON THE NUMBERS, WE ARE SIMPLY
24       PUTTING A SIGNIFICANCE ON THE  PRESENCE OR  ABSENCE
25       OF THE  CHRYSOTILE, WE ARE PREPARING TO GO BACK,
                                316

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        WORKING WITH THE PROJECT  OFFICERS, TO RESAMPLE SOME




2       OF THE SUBCATEGORIES,  TO  ENLARGE OUR DATA BASE,




3       AND TO TRY TO MAXIMIZE THESE  METHODS IN THE




4       DETERMINATION OF ASBESTOS IN  THE WASTEWATERS THAT




5       WE ARE INTERESTED  IN,




6         ARE THERE ANY QUESTIONS9




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                                  -11L

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                         MR, DAVIS:  ABE DAVIS,
HOOKER CHEMICAL,   ONE VERY TRIVIAL QUESTION; HOW
ARE YOU DIFFERENTIATING CHRYSOTILE FROM ANY
OTHER TYPES OF ASBESTOS?
                         MS. HOLTZCLAW:  WE'RE
USING SELECTED AREA ELECTRON DIFRACTION,
                          .118.

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                                  MR,  TELLIARD:   THAT BRINGS



 2       TO AN EXCITING  CONCLUSION ANOTHER ONE OF THESE,



 3       I'D LIKE TO  THANK  YOU ALL FOR COMING,   I'D LIKE  TO



 4       THANK THE  INDUSTRY PEOPLE FOR PARTICIPATING,   I'D



 5       LIKE TO THANK OUR  OWN PEOPLE  FROM BOTH  THE REGIONAL



 6       LABS AND FROM THE  R&D LABORATORIES FOR  TAKING THE



 7       TIME TO COME UP AND ALSO  FOR  THE HELP THEY'VE BEEN



 8       GIVING US  OVER  THE LAST YEAR,  THIS IS  THE THIRD



 9       IN A SERIES,  WE DID HAVE A COMMITTEE MEETING



10       LAST NIGHTJ  WE  DID JUST MAKE  SOME VERY  LARGE



        DECISIONS,   WE  DECIDED THAT THIS TIME THE PROCEEDINGS



12       COVERED WILL BE READ, AND  WE HOPE TO HAVE THEM OUT



13       A LITTLE BIT FASTER THAN  WE DID LAST TIME,   THANK



14       YOU AGAIN  FOR YOUR ATTENTION  AND THANKS FOR COMING,




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                                .319.

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