&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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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.
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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
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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
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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
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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-
oc
o
*
LLJ
Q
LU
CD
<
OL.
O
££
o.
10-
8-
6-
2H
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
-------
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
-------
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.
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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
-------
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_
-------
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
-------
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
-------
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
-------
, 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,
-------
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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tsi
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cn
2
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o
100. DO,
87.50J
75.00J
62.50J
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OTTOS 2T&5 5^04
i'o.03 i.&3 iB-3 i&2
T I ME f M I N )
550 . . 600
z's-oi27-.so, •• so.oq •'(}• *•''.'"'. |
-------
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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YERSTON"OT-r;
-------
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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-------
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
-------
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
-------
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
-------
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
-------
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
-------
138
-------
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
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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
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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
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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
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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
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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
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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
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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,
-------
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
-------
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
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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;
-------
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.
-------
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.
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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
-------
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
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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
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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
-------
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,
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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,
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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
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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
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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,
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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
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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.
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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.
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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
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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
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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
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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
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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
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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.
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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.
-------
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
X-RAY FLOURESCENCE SYSTEM
1024
Channel
Analyser &
Display
Stop
Reset
Multi
Reset
Sample
Indexer
PDP-11
Computer
__
[ Plotter
1 or
I Printer '
I 1
Start*
End*
*(of Data XFR from analyzer
to PDF)
V
Mag. Tape
TeleType
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
3.O
22.0
a:
< 1.0
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r ffiUJitJj
TFlPr'lJft.f'ff •!' * • * «•
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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
-------
N>
3.0 >-
2.0
o
h-
(T
1.0
UJ
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
-------
""• -,
>:;
V, T
->-6L
lf\
v»
'•^....
/
1
• I .
» :! " •
: s 5 ; -
• * •
• ! ' - .
• • •
« . ! •
• . i •
• : •:*»
• I -! '
• • • .
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i S
! !
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
-------
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
-------
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
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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.
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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
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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
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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
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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,
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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
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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
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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
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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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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
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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,
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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
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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
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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
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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
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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
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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,
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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
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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
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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
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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
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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,
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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,
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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
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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,
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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,
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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
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
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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,
15
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