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FALS-VP PAGE &

CALIBRATION FILE: ¢

’

“DATA FILE NAME:

“TITLE: 7

PMASSCES3: 7

7INTEGRA. TIME: 7

“MASS OUTSIDE CALIBRATION RANGE. ¢


Zero block counter

Get current address

Subtract buffer
start address

Increment block counter

Subtract 201(8)

No
Increment
block
counter
Write data
(Subroutine
WRTDAT)
Reset buffer
pointer and
counter
[ Write EOF ]
Write data
: (Subroutine
. WRTDAT)
ah T
"Reset buffer
pointer
Return

FIGURE 9, FLOW CHART FOR DATA-BUFFER-PROCESSING ROUTINE

22


RESEARCH REPORTING SERIES

Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:

1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research

4. Environmental Monitoring

5. Socioeconomic Environmental Studies

This report has been assigned to the ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.

EPA REVIEW NOTICE

This report has been reviewed by the Office of Research and
Development, EPA, and approved for publication. Approval does
not signify that the contents necessarily reflect the views
and policies of the Environmental Protection Agency, nor does
mention of trade names or commercial products constitute
endorsement or recommendation for use. ~


7SYMSCN PALE-VP PAGE 11

IFZERO PLIST <HLIST> @RESET IF NOT LISTING PLOTTER ROUTINES
“SUBROUTINE TQ GET DATA FILE NAME AND
PDETERMINE WHETHER THERE IS ALREADY A FILE
“BY THAT NAME ON THE SYSTEM DEYICE
@4322 GOOG RDFILE, @

@4323 4437 ums . APL ¢PRINT "DATA FILE NAME: "
@4324 3244 TEXT2
@4325 oa14 16
@4326 1656 RDF41, TAD ATTRDI
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@4338 4457 ams I DSPF
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@4332 3527 DCA I TTIRD eDISABLE TTY REAL
94333 4562 uns I OFENWX DOES FILE EXIST>
@4334 Sé6aa LINE ¢FILE NAME ADDRESS.
@4335 6600 BUFG@
84336 Sid4 JMP +6
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@4344 4612 12 .
O4342 4442 gms I AGUES @PRINT "?3"
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G4344 4454 ams I ATRANS /MOWE FILE NAME
Q4345 4353 RDF2
B4346 GG63 3
G4347 S342 JMP 275 “ERROR RETURN
64356 7408 NOF
O4351 4464 ums 1 HDRELK
4352 S22 vMP I ROFILE
Q@4353 G8GG RDF2, U7]
94354 Gooa a
4355 aoa a
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@4356 406 RCGCHR, @
@4357 4466 uMS I ENPCKI INSERT RECORD END
4366 7171 eir7t CEGF FLAG
64364 4436 ums 1 AINTOF “TURN GFF MS INTERFACE
G4362 4537 ams I APENUP /RAISE PLOTTER FEN.
64363 6604 ION
B4364 4454 ams I CLOSEX CLOSE FILE
@4365 4353 RDF2
64366 S6aa LINE
44367? G6G6 a
@43768 7416 SKP CERROR RETURN
@4374 5376 JMP TERMIN
Q4372 4524 ums I TCHCKI
64373 4448 ums I APLR ¢PRINT "CLOSE ERROR!"
64374 3165 TEXT16
$4375 aoa6e 6

4376 4524 TERMIN. JMS I TCHCKI
64377 5464 ume 1 EXECK ’


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TIMSTL
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TRTIME
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TTYOUT
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a

Vi ‘Set calibration mass
pointer (ADMAS)

Set calibration voltage
polater (ADSET)

‘Set input buffer
pointer (CBUFF)

[cer fi cary ]
apt

Tie
Tron print

[Se mat] -eatbration fe exe
Tae
pan [eeu |

Toerement

Anpa potter
by3

Get fire
{[Leattbration word

‘Shift eight
4 places tate.
MQ

Tocrement
Input polotes

‘Ada 2nd
‘eattbratton |
word tw AC.

Tnerement CALBUF

FIGURE 3. FLOW CHART FOR CALIBRATION-FILE-PACKING SUBROUTINE

12


/SYMSCN PALES-¥? FAGE 415-2

TAD EATPAL

FING: ASESML GET SIGN BIT
OCA ASEM

TAD I ASRSM NUMBER CF SHIFTS
oCA +5

sz ASESM UPDATE RETURN
TAD EAETFA

AND ASRSMS

LSR

(3)

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> MF I ASESM
ASRSM1, 4608
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vMP I DPICSM >


. aM

a -0,04 ng DDT b-0.2 ng Dieldrin c-0.2 ng DDD d-O.! ng Parathion

FIGURE 14. SIM PLOTS FOR CI GC/MS OF PESTICIDES
Carrier Gas: Methane 30 ml/min
Column Temperature: 175-250° C @ 10° C/min
Column: 6 ft. x 2 mm glass, 3 percent
OV-17 on Gas-Chrom. Q

29


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IFNDEF ERE < EAE=@ >
IFZEROQ ERE <¢

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; muysM

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IFN2RO ERE ¢

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?

“SYSTEM 156 DEFINITIONS:
é

LINE=5666
RAD=266

MON=464
READ=MON+12
OPENR=MON+264
GPENW=MON+242
HAIT=MON+46@
TTY IN=MON+1 G86
TTYOUT=MON+1461
CLOSE=MON+266
WRITE=MON+4
EXEC=MON+60@

PAGE 2-1


“SYMSCN

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PALE-V? PAGE 9-2

P24, fed
QUERY, @ PGUESTION SUBROLITINE.
TAD ATTROI
DCR I TTRD “ENABLE TTY READ
oMS I AINFL READ ANSWER.
DCA I TTRO @DISRELE TTY INPUT
TAD I ALINE /¢GET ANSWER
AND PRPG@G MASK CFF FIRST & BITS
TAD YNEG PSUETRACT "y"
SNA CLA
UMP I QUERY = /FOSITIVE RETURN.
182 QUERY
UMP I GUERS “NEGATIVE RETURN.
NEG, 4700
Prrag, Free
/SUBROUTINE TO WRITE HEADER BLOCK.
HDBLOK, @ .
UMS I WRITEX WRITE TRIPE HEADER BLOCK.
q
20a ONG. WORDS.
RAD “WRITE START ADDRESS.
a “DONE FLAG
UMS I WAITS
CLA

Jas 1 TCHCKI
JMF I HOBLOK


1.

SECTION VII

REFERENCES

"Mass Fragmentography. Identification of Chlorpromazine and its
Metabolites in Human Blood by a New Method", G. G. Hammer, B.
Holmstedt, and R. Ryhage, Anal. Biochem., 25, 532 (1968).

"Mass Spectrometry of Crude Biological Extracts. Absolute
Quantitative Detection of Metabolites at the Submicrogram Level",

A. A. Boulton and J. R. Major, J. Chromatography, 48, 322-7 (1970).

"Rapid Identification of Low-Molecular Weight Compounds in Extracts
of Biological Materials, C. G. Hammar, B. Holmstedt and R. Ketz,

J. Chromatography, 49, 402-8 (1970).

"Determination of Chromium and Beryllium at the Picogram Level by
Gas Chromatography-Mass Spectrometry", W. R. Wolf, M. L. Taylor,

B. M. Hughes, T. O. Tiernan, and R. F. Sievers, Anal, Chem., 44,
616-8 (1972).

“Smoothing and Differentiation of Digital Data by a Simplified
Least Squares Procedure", A, Savitzky, and M.J.E. Golay, Anal. Chem.,
8, 1627-38 (1964).

"Quantitative Mass Spectral Determination of Morphine in Body Fluid
Extracts", P. A, Clarke and R. L. Foltz, Conference on Stable
Isotopes in Chemistry, Biology and Medicine at Argonne National

Laboratories, Chicago, Illinois, April 1973, Clinical Chemistry,
in press.

D. Catlin, R. Cleeland, and E. Grunberg, Clinical Chemistry, lg,
216 (1973).

32


“SYMSCN PALS-V? FAGE 18-2

@2722 FEBS DCA SIGN “CLEAR SIGN SWITCH.
@2P7ss 1268 TAD DIVIs ?GET BACK OPERAND
@27z4  5P2G UMP oI STGML “RETURN,
Q@3735 G8G8 SIGN, a

1f
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ee
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@2745 3268 : DCA OIVIa “STORE MSH ANSWER,
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BE755 Srd4 VHF 1 SIGNS -

é
¢ ONE OF THE ERE SIMULATOR ROUTINES.

IFZERQ EAE <

LSRSM, @

DCA EAETP2 “SAVE AC

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1s2 LSESM

S2A eNO) SHIFTS?

TMP tz

TAD EAETF1 “RESTORE AC

IMP I LSESM

CIA “COMPLIMENT

DCA ERETP2

TAD EAETP1 “RESTORE AC
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SWF “GET LOH

RAR “ROTATE

SUP

Isz EAETP2 “DONE?

vir LSRLP “Ng

oMP I LSREM >


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CONNT

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L
TMP
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THES

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PAT
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DPM?
ae

3600 FAGE

PAGE 9-2


“SYMSCN

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ACLBUF,
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“CHKSTI,

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eed
PAGE

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JM
CALBUF
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DCONST
MSSET
a
NTCATA
FLOTPT
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PLTFCT
RUNTIM
a
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~175a@
~1265

PALE-VP FAGE 3-2

FNTLEN “NC. LOCATIONS PER SET.
ADSTOR NEXT BUFFER LOCATION.
CYCLEL


“SIMPLT. ‘ PALSY? PAGE 3-2

G2455 3765 DCA I Peat.

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92175 G@227 327

@2i7é G244 A244, 244
é?

@a17r? 3566
2260 FAGE


SECTION IV

The System 150 provides standard programs for data acquisition and dis-
play. These programs are ideal for gas chromatographic data; they
provide output of real-time and reconstructed gas chromatograms as well
as mass spectra plots. However, the standard programs are designed for
discrete mass spectra, If the operator elects to monitor only one ion,
an entire block of data is recorded for each point, so that a large

amount of file storage room is required.

For electronic signals with random noise, the signal-to-noise ratio in-
creases as the square root of the observation time,

s/n = kWe .
For example, consider the comparison of an ion in a standard mass spectrum
(3 sec. scan, 300 amu) with monitoring of a single peak (100 msec inte-
gration periods) for a standard mass spectrum 10 msec is spent on each
peak, but 2.3 msec is required forsettling time between masses, so 7.7
msec is the actual integration time. For the SIM technique, the inte-
gration time is 97.7 percent of the total time, Hence the expected

signal-to-noise ratio improvement is given by:

8/N = V.977x3x1000/7,7 = 19.5

The standard System 150 routines are not well suited for the SIM technique.
For disk systems, the large amount of storage space is not a major
obstacle, although only a few runs can be made before a disk will be full.
For a DECtape system however, it is a major problem. It is not unusual
for a gas chromatographic run to last 30 minutes, and for 1 sec integra-
tion times, 1800 spectra would be acquired; a DECtape will only hold at
most about 1200 spectra (1472 blocks, but about 250 are required for

system programs).


CONTENTS

Sections
I CONCLUSIONS

IL RECOMMENDATIONS
III INTRODUCTION

IV. COMPUTER PROGRAM DEVELOPMENT

Vs SYSTEM PERFORMANCE

VI REFERENCES
VII = APPENDICES

ili

Page

own

29
35
36


oSYMSCN PALE-VE PAGE 2-4

G@hidt 4237 ACRON, CRON
Gaid2 4246 ACRUP. CRUF
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@G@idée 4262 ACHLCU, CHLCUP
Gadd? 4344 ACHRCO. CHRCON
Goi5o Free SPTBUF, PLTBUPF
GGi541. guna EAETP1, &
BG152 G08 EAETF2, &



“STMSCN PALS-Yr PAGE 15-1

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MDV4AS, -45
CCMSM. = &
DCA EAETF4 STORE. MSH
SWF “GET LSH TO AC
CMA CLL CML IAG ¢COMFLIMENT AC SET LINK TO ZERG
SWF CIF AC WAS ZERO
GLK GET LINK BIT
TAD ERETP2 “AGG TO MSH
CIA “COMPLIMENT
JMF I poms”
DLDSM, @
cAM ‘CLEAR AA, MG
TAD I CLOSM “GET ADDRESS
DCA tz
Isz CLEeSM “UPDATE RETURN
DAD “DOUBLE ADD TO A CLEAR AC, Me
a
oMP I GLOSM
BUF a=
+BUFG+1 205
DADSM, @
, DCA EAETP4 STORE AC
TAD I DADSM ?GET ADDRESS OF LSH
DCA EAETF2 /STORE
Is2 DADSM “UPDATE RETURN
CLL .
. SHP (SWAP MG, AC
TAD: I EAETP2 ¢LSHC1)+LSHC2>
SWF fPUT IN MG
GLK @GET CARRS BIT
1sZ ERETP2 /MSH ADDRESS
TAD I EAETF2
TAD ERETFA = ¢MSHC4A24+MSHC2)
JMP I CADSM DONE.
ASRSM. @

DCA EAETFL “STORE MSH


/SIMPLT. PALS-¥7 PAGE 2-1

oeG6a 3777 377?

G6661 G69G SPCADL, @

G@G62 G66G RESET, &@

G6G63 3616 AYPLT, YRGC

@eg64 3667 AXPLT. -XRGC

40065 GaGG FENUD, @

@@G66 2357 ATRNON, TRNON

a16@ +1408

“GENERALIZED PLOTTING PROGRAM, ALL MEASUREMENTS .IN TERMS
fOF PLOTTING INCREMENTS ¢.@4°S>. NO SCALING DONE BY PLOTTING
7FROGRAM

“VARIABLES
66160 geen x, &
B0104 gona YY. &
@a162 G00 FACT. @
NUME,
LL.
96163 GuGG SADDR, &@
LJ,
G8144 G60 THETA, @
LXADDR,
4185 aaon Ss, @
LYADDR.
@4166 G666 Dx, &
LK,
$0197 BEGG XMIN, @&
DTIC,
60119 608 LN,
96114 go6a Ix,
0112 Gooe I¥,
$4113 GBoa AX
G6414 4600 AY,
96115 9686 Bx,
6614146 g080 BY,

Qeooeea

@LINKS AND POINTERS

60417 4266 ADPLOT, FLOTX

661428 4466 ADPFTCH, PFETCH
G@@i24 4542 ADSBAL, SUBALF
$6122 4518 ADMULT, MULT

@4122 4446 ADNEWB, NEWB

$6124 4667 ADLTR, LETTER

46425 4726 ADRTAT, ROTATE
6126 4607 OUTPUT, LETTER

@CONSTANTS
SG427 BOT? NP? 7?
9613@ 77G4 MP?, -77
961434 @885 NS. 5S
96132 G@614 N44, 44
S@132 6144 Nidd, 144
94134 7774 M4, -4
84135 7776 Me, -2
64136 7775 MZ, -2


EPA-660/2-74-004
January 1974

Environmental Protection Technology Series



*/SIMPLT. PALS-V¥P PAGE 11-1

TAD CIYSOR
f2b
DCR EAETPL
CLA
bY2, TAD ERETF2
RAL
BCA EAETF2
Isz DIVCNT
IMF DYE
TAD EAETF2 “GUOTIENT
SWF “TO Mo
TAD ERETF4
CLL
UMP I BYISM
DIYSOR. @
DIVCNT, &
MDYV43, -415
SHLSM, &
CCA EAETPL
TAD I SHLSM “# OG SHIFTS
IszZ SHLSM “UPDATE RETURN
S2A eNO SHIFTS?
JMP .+3
TAD EAETPL RESTOR AC
vMP I SHLSM
CIA
OCA ERETF2
TAD EAETPL
SHLLF. 9 SNF “GET LSH
CLL RAL “ROTATE 1 BIT LEFT
SNF “GET MSH
RAL “ROTATE 1 BIT LEFT
Isz EAETF2 “DONE?
UMP SHLLF
vMrF 1 SHLSM “YES - RETURN
LSRSM. @
BCA EAETFL “SAVE AC
TAC I LSESM “GET NUMBER OF SHIFTS
Is2 LSRSM
SZA “NQ SHIFTS?
JMP .ts *
TAL EAETPL “RESTORE AC
uMP I LSRSM
cIA “COMPLIMENT
DCA EAETP2
TAC EAETPL “RESTORE AC
LSRLP, CLL RAR “ROTATE MSH 1 BIT
SWF “GET LSH
RAR “ROTATE
SUF
Isz EAETPS “DONE?
TMF LSRLP | “NO

uMF I LSRSM >


ABSTRACT

Computer programs have been developed for a PDP8/e controlling a Finnigan
1015 quadrupole mass spectrometer to monitor selected ions from components
in a gas chromatographic effluent. The program is designed to monitor
only a few ions (1 to 8) to enhance the sensitivity for the selected ions.
Signal-to-noise levels of 19:1-30:1 have been obtained for 0.2 ng or less
of A eddies eripfoying chemical ionization mass spectrometry and a

TRG -smodthing routine.

Bera 8 Ga Hetses i

This report was submitted in fulfiliment of Project Number 16ADN 28,
Grant Number R-800909, by Battelle Memorial Institute under the sponsor-
ship of the Environmental Protection Agency. Work was completed as of
June 30, 1973.

Li


@SIMPLT. . PALE-¥7 PAGE 12

IFZERO PLIST <XLIST> “RESET IF SKIPPING FLOTTER LISTING.
Ce .
54@@ PAGE


The SIM technique is especially well-suited to analysis of very small
quantities of known materials. Since the analysis is based on only a

few ions, sensitivity is gained at the expense of the specificity of a
complete mass spectrum. However, since it is generally intended for

use in gc/ms, retention times provide additional confirmation of identity.
Chemical ionization (CI) mass spectrometry is especially suitable for SIM
because it is generally more sensitive than electron impact (EI) mass
spectrometry and because CI spectra usually show less fragmentation than
EI spectra, Accordingly, the development work on this project has been
done with CI mass spectrometry. Four pesticides have been studied in

the evaluation of SIM.

The EI and CI (CHy) base peaks for these pesticides are tabulated below:

Pesticide M/E
EL CI
DDT 235 243
DDD 235 209
Dieldrin 79 279 (243 is 50% of 279)
Parathion 292 292

The spectra of the chlorinated pesticides show significant fragmentation
under CI conditions, but better sensitivity is obtained with CI than EI
conditions, EI and CI spectra for p,p'-DDT are shown in Figure 13,

Figure 14 shows SIM plots for CI gc/ms of the four pesticides, 0.04 ng of
DDT, 0.1 ng of parathion, 0.2 ng of dieldrin, and 0.2 ng of DDD. Signal-
toenoise levels for these chromatograms have not been determined accurately
but are approximately:

Pesticide S/N

DDT 15:1
Dieldrin 10:1
DDD 1231
Parathion 30:1

27.


“SIMPLT. . PALE-VF PAGE 4-1

P44s DAL
Geee LOCHK, &@

SMA
oMF DONECK ANC GOCE:
CAM
TAD SPCADE
OCA J+ \
CLD
a
OST
LWINT

DONECK, CAM
ISz NETS

B2303 JMF +

#2204 gms 1 AEBLKL ECE

B2265 ums 1 ROINTS
Berg6 TAD RESET
G2207 OCA SPCADE
JMF SURVEY-Z
TAD I APZaTS2
CIA
DCA PaeTL
62a INCRLP. CAM
2H64 ISZ SPCADL
2664 IsZ SPCADE
2337 Isz Pa2T4
Pai SKF
5235 uMF SURVEY
16e4 TAC SPCAGL
2225 CCA +2
PEGE DLE
eae a
75aa SMA
S344 IMF INCRLF
S?24 JME 1 EREFxL ECR OR ECF

2430 EREFN1. EQRECF
2554 AEBLK1, EGELOK
G@2z32 60H APLTIT. Zéan
2334 2400 ASRERL, 2400
G@23z5 2466 APZGT2, FZaTS

G@2336 GHGG NPTS1, @
G@2337 GHGG F22T1., a
2246 G@641 MES4, aé614

G2341 1465 1485 “FILE

92342 PP4a 774

@2%43 G2zi0 MES2, G316

G@2i44 @416 Gite

B2245 e7as areas “CHANGE FEN
B2i4d6 4020 4020

Baz47 O5416 @516

92356 1265 FPL265, 1265

92351 9000 SETMSP, @

2252 42355 TAD z200a
@2252 756 DCA I AXMSCL


eSIMPLT. PALE Vr PAGE 2-3

rae? OVI=T4a7
PSPS OCMSrsrs
F4GS MUY=F4a5
Fai? LSR=?44?
P4iz  SHL=?4135
P4510 DPSZ=F7454 >


Mass storage
data
recording

Start

Initialize system, input
masses, integration
times, run time,

file names, and title

Control mass spectrometer }wq—— Keyboard
. “" operation P| monitor
Real-time data. End
plotting
FIGURE 1. GENERAL PROGRAM FLOW CHART



/SYMSCN
g2668

azé661
az662
62663
a2664

2665
G2666
a2667
82676
2674
2672
62673
aze74
82675
G2676
a2677

e270
e2704
a2z7a2
92702
az7a4
@2785
a2706
e2707
@2710
o2744
62712
@2743
02714
82715
62716
@2747
a2728
a2724
62722
02723
e2724
@2725
02726
02727
82730
62734
82732
02733
@2734

2666

1264
3764
576a
2617

4445
4464
77a
6aa4
4464
6ag2
4434
1456
2527
S677
2066
278@
4427
4424
4442
532a6
3477
1477
7044
11425
77aa
S314
4442
5386
3527
7348
1477
3374
1374
7458
S327
?424
74as
3065
7524
4442
3443
1374
7458
534@
7424

NCHRET, MCHAL

PRLESV7 PAGE 6-1

“CHANGE PLOT SCALE FACTOR

FCHANG, TAD
DCA I
JMP oT

FCHRET, END

FCHRET
APLTFC

fRETURN ADDRESS

APLTFL “CHANGE PLOT FACTOR.

?CHANGE MASSES TO MONITOR,

ENTRY OF NEW SETS CF MASSES DURING OPERATION IS NOT
/FOSSIBLE WITH THE NON EAE YERSICN UNLESS THE PROGRAM
71S ALTERED TO CALL FRONYT AS AN OVERLAY

MCHANG,
IFZERO EAE <
JMP END >
IFN2ZRO EAE <
gms I ASTINT
MCHA, JMS I ENDCKI
rare
IGN
gas 1 HDRELK
IaF
gms I AINTON
TAD ATTRDI
DCA I TTROE
JMP I th
RESCAN
SCHANG=
MCHAZ, JMS I AINPL
JMS 1 ADEG
JMS 1 AQUES
JMP MCHAS
bcA I NSET
TAD I NSET
CIA
TAD TOTSET
SMA CLA
JMP MCHA
gms I AQUES
IMP MCHA
MCHA4, DCA I TTRO
NL? PP?
TAD I NSET
DCA SDIFF
TAD SDIFF
SNA
JMF MCHAS
ACMC
muy
P2@
SWP
MCHAS, TAD RODLOC
DCA RODSTT
TAD SDIFF
SNA
UMP MCHRE

ACMC

SCREINITIALIZE POINTERS.

(WRITE NEW HEADER BLOCK.
?TURN MS INTERFACE ON
“ENABLE TTY REAC,

“READ SET NO.

“TRY AGAIN

“NUMBER TOO LARGE?
7NG. NUMBER CK
CPRINT “23

“TRY AGAIN
“DISABLE TTY READ
fACS-4

“GET SET NG.

PNG, O47
fNG, ! USE FIRST SET.
“PUT IN MG

“PUT ANSWER IN AC
“START GF VOLTAGE ARRAY
@START CF THIS SET

7SET NO. 347
7NQ. USE FIRST SET.
fPUT IN MG


/SIMPLT,

HEE

Bon RGCELT,
aod

a2

BS

aod

Bas

aes ;

aa? MEGC.
846 YRAC.
44

RTNORIG.

BOBS
gage

RTNRG4,

ROHEDR,

ams 1

CMA

PALS

TRGC
FRGCPLT
FENLIC
ADFLOT

RGCPLT

ADPLOT
ORGNiIM
RESYRG
YRGC
YRG
YRGC

SRGC
RGCPELT
OR GNUM

PENLID
AESYRG

+4

AGPLOT

AOPLOT
PENUD

RTNOEG
ADPLOT

ADFLOT
RTNRGA

REALS

eo VALUE

CNEWM OR ITRGIN

“NEM ORIGIN

PAGE ?


“SUMSitN

S5656
e565?
aséea
e5éed
a5ée2
G5663
greed
g5665
a56e6
B5667
asera
aserd
Onér2
G567z
aser4
a5675
O5676
a5677
95764
o5761
O57a2
85762
g5704
a5765
95706
95767
a5746

PALS-VP PAGE 16

IFZERQ EAE < *64@a >
IFNZRO EAE < #564@
BUPE=688G > .

“DECIMAL TO GCTAL FRACTION CONVERSION ROUTINE
eTHIS ROUTINE IS OVERLAIC &Y THE DATA BUFFER

“IN THE NON EAE VERSION. THEREFORE. NEW SETS OF
“MASSES CANNOT BE ENTERED CURING A RUN LINLESS
“THE PROGRAM IS CHANGED TO CALL FRCNYT AS

“RN OVERLAY WHEN NEEDEL.

FRONYT, @

OCA FRNCTE
OCA FRTEMF
FRCNd, JMS I AGAC “GET A CHARACTER:
TMF FREXIT NC MORE CHARACTERS.
TAD MPL
SMA S2A “GT. 710997
TMF FRESTL NC
TAD Nit :
SPA 7GE. 68 Cho?
IMF FREXTL NC.
DCA FRCOFCT
TAD FRNCTR:
TAD FRNIMP
ocA tt
FRON2, HLT (CHANGED TO JUMP,
TAD TENS
TAD HUNDRS
TAD THOUS
ACNKC “PUT IN MG.
Muy
FRCFCT
MGAC 7GET ANSWER.
TAD FRTEMF /PREY. TOTAL.
DCA FRTEMF /NEW. TOTAL.
IszZ FRNCTR
NL??? 75 fACH-z
TAD FRNCTR
SFA SNA CLA 71ST OR 2NC CHAR?
IMF FRONS fVES. TRY ANCTHER.
gms 1 ACEC 7NQ. GET REST. IF ANY.
oMP .+é 7END OF LINE.
NOF
FREXIT, CLA
Isz FRCNYT INCREMENT RETURN
TAD FRTEMF ¢GET NUMBER,

JMP I FRCNYT /NORMAL RETURN
FREXT4, CLA

TAG FRNCTR

SZA CLA CANY CONVERSION?

IMF FREXIT /YES.


SECTION VILI
APPENDICES

A, Listing of Data Acquisition Program

B. Listing of EAE Program

33


/SYMSCN FALS=<VP PAGE 4-2

92353 S652 UMP I CALIE
@2354 @00G INTDIF, @
@2355 @66G MASDIF, @
G2356 7466 ADCMAS, CMASS
@2z357? 754@ ACALST., CALSET
@z2z6G @600 ADMAS2, &@
PSUBROUTINE TO SET POINTERS BEFORE CALLING SETCAL

@2361 @600 PRESET. @

62362 41417 TAD TADMAS “SET MASS POINTER
G2362 3024 DCA ADMAS.
62364 1523 TAD I TMASS
2365 7a44 cla
G2366 2a7s OCA MNMASS
@2367? 144% TAD RODSTT
G237a 3772 DCA I RODADI
@ax7i 5764 JMP T PRESET
$2372 3762 RODADI, RODADD
vee

2404 PAGE


eSIMPLT.

XMIN
SMSCLR
RRGC

y

YHD
YMSCLR
YRGC
YTOBPL
2eQAR

aia?
27ia
sag?
@ied
3345
2732
2618
2636
e355

PALS-¥?

U8, GOVERNMENT PRINTING OFFICE: 1974

PAGE 19-2

546-317/314 1-5


“SYMSCN

92608
e26a4
62662
82603
g26a4
S268a5
a2686
62667
42616
@2644
92612
92643
62644
42615
g2616
@2647
92628
@2624

92622
92623
2624
82625
82626
92627
G2638
G2634
G2632
G2633
92634
82625
G2636
82637
$2646
92644
92642
92643
92644
92645
G2646
92647
82658
92654
62652
82653
62654

@2655
62656
62657

PALS-V7 PAGE 6
2600 «2600 ‘
(SUBROUTINE TO INTERPRET TELETYPE
COMMANDS DURING OPERATION
@000 RDKYBD, @
6036 KRB READ TTY KEYECARD.
3372 DCA STORE
4430 UMS I AINTOF /TURN MS INTERFACE OFF.
1372 TAD STORE
6004 ION
4773 uMS I ATTYT = CECHO.
1056 TAD ATTRDI
3527 DCA I TTRO ENFIBLE TTY READ.
4372 TAD STORE
1362 TAD MEE MINUS E.
7648 SZA CLA ¢IS CHARACTER E?
5225 oMF CHANGE /NC
5222 UMP s STOP VES. TERMINATE RUN
4756 RDK1, JMS I CRLF ¢PUT OUT CRLF
6062 END, 10F
4434 UMS I AINTON TURN MS INTERFACE CIN.
5600 IMP I RDKYBD
ROUTINE TO TERMINATE DATA ACQUISITION
7AND START PLOTTING. ;
4427 STOP, JMS I AINPL /WAIT FOR CR
6002 10F
5443 JMP I ARGCHR
4372 CHANGE, TAD STORE
436% TAD MCNTRL 9 ¢MINUS CONTROL-L.
7458 SNA 71S IT CONTROL-L?
5254 oMF ABORT YES. ABORT
41364 TAD MESS ?MINUS S.
7456 SNA ¢1S CHARACTER S$.
5300 IMP SCHANG -/YES.
41365 TAD MTEE ¢MINUS T.
7456 SNA 71S CHARACTER T?
5354 oMP TCHANG YES.
1366 TAD MEN ¢MINUS N
7456 SNA 71S CHARACTER N?
5255 IMF NCHANG YES.
1367 TAD MEM MINUS M
7458 SNA 71S CHARACTER M?
5265 IMP MCHAING YES
42378 TAD MEFF MINUS F
7658 SNA CLA 71S CHARACTER FF
5264 oMF FCHANG § YES
5216 oMF RDKL ¢NG. IGNORE.
6002 ABORT, I0F
4537 JMS I APENUP “RAISE PLOTTER FEN
6601 ION
5461 UMP I EXECK / AND RETURN TO EXEC.
CHANGE NUMBER OF POINTS USED IN
_ /COMPUTING RUNNING AVERAGE.
4260,4,.NCHANG, TAD NCHRET RETURN ADDRESS.
34364 DCA I ANPNTS.
5757 UMP I ANFNTL /CHANGE NC. FOINTS


“S9HSCN . PRILE-V? PAGE 5
2400 #2408

“INTERFACE CONTROL FOR SYSTEM Sa@“15a/25a MASS
/SPECTROMETER INTERFACE.

“THESE ROUTINES TURN THE INTERFACE

“FISED SAMPLING PERICG® ON AND OFF. ALLOW THE
“TIME REGISTER TO BE LOADED AND ALLOW A DOUBLE
“PRESISION NUMBER TO BE SENT TC! THE MASS SET

“REGISTER.

?THIS SET OF ROUTINES WAS WRITTEN Bt:
é Wo od. FIES

? FINNIGAN CORF.

7 595 N PASTORIA AVE

é SUNNYVALE, CALIF.

? 488-P 32-946

“THIS VERSION DATE: 42-28-74
“ADAPTED FOR MASS MONITORING PROGRAM BY:
° M. 6. NEHER
? BATTELLE MEMORIAL INSTITUTE
é S@5 KING AVENUE
é COLUMBUS, OHIC 43261
“TURN INTERFACE INTERRUPT AND FLAG OFF
“CALLING SEGUENCE:
? IMs INTOF
“RETURN IS TO JMS+1
82406 GaGa %$INTOF: @

G24a1 Frae CLA CLL
Hedge ered MSI “SEND ZERQ TO LOWER IER
2483 CLA
B24a4 TAL K34@
a24a5 MSI “SEND COMAND CODE TO UPPER &
a24a6 CLA
G24a7 Séae IMP 1 INTOF “VES, NOW RETURN.

“TURN INTERFACE INTERRUPT AND FLAG ON
/CALLING SEGUENCE:
é IMs INTON
“RETURN IS TO IMS+4
S2416 @686 INTON @

g24i4a CLA IAC

B2dd2 MSI “SEND 4 To LOWER IBR
S241 CLA

Hadid TAD E34

ge4i5 MST “SEND COMMAND CODE TO UFFER BE
gediée NLP? Pe fACSe4

a2417 OCA WTFLAG “SET WAIT FLAG

2426 3626 DCA I INTONS

2424 44234 TAD WAITL ?SET UF DELAY

Be422 2227 DCA WCOUNT

B2425 2227 IszZ WCOUNT DONE?

G@2424 5225 UMP oct eNG. WAIT LONGER.
@2d25 5614 uMr ot INTON

G2426 4435 5 INTONL, PLOTPT

2427? BGaGA WCOUNT, &
7SEND INTEGRATION TIME
“CALLING SE@UENCE


7SYMSCN

ABORT
ABUFG
ACALIB
ACALST
ACHLCD
FICHLCU
ACHRCD
ACHTLF
ACHTRT
ACLBUF
ACM
FICRDN
AICRUP
ADCMAS
ADE
ADEO4
AIDMASS
ADMAS4
ADMASZ
ADPLTW
ADSET
ADSTOR
ADTIME
AIF AICT
AGAC
AINPL
AINTOF
AINTON
AIL INE
AMASS4
AMPPTR
FIMSSET
FINPNTS
FINPNT4
APENDN
AIPENUP
APL
APLR
APLTFC
APLTFA
APNUM
AGQUERY
FIQUES
ARDF IL
AARGCHR
ARNT IM
ASETT
ASR
ASTCAL
STINT
ATIME
ATIMS4
ATMSET
ATRANS
ATTFRI

2654
ea26
S776
2357
6145
4146
614?
143
6144
2164
7424
61441
G1id2
2356
6621
6622
6023
e424
2266
4475
2233
6625
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4575
S7r2s
az?
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66341
4632
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GO34
3462
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2757
4146
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6046
2764
2766
go44
2463
oa4d2
2164
6843
2474
Gadd
7445
6635
6445
Bade
2754
3664
4054
oad?

ATTRDI
ATTYT
BFLAG
BSET
BUFEND
BUFLOC
BUFSET
BUF a
CALBUF
CALIBE
CALSET
CAM
CBUFF
CBUFFL
CHANGE
CHKSET
CHKSTI
CHLCDN
CHLCP41
CHLCUP
CHLC41
CHRCDN
CHRCL
CHTLFT
CHTL1
CHTRT
CHTRL
CLOSE
CLOSEX
CMASS
COMPAR
CONFIG
CRDN
CRDNL
CRLF
CRUP
CRUPL
CTR
CYCLES
CYCLE2
DAD
pcm
DCONST
DCONTI
DEO
DEO4
DIVIDE
DIVIDI
DIVIL
DIVI2
DIVIS
DIVNUM
DIVSET
BLD
DONE

ease
277s
3165
a244
e172
ease
2u74
eaaa
2206
2252
75a
7624
CEE
2215
2625
44a
Z473
4272
4346
4302
4304
4344
4247
4255
4263
4264
4272
aene
aes4
74aq
4447
3164
4237
4245
2756
4246
4254
4572
2104
2105
744z
7575
3608
2162
s2aa
520a
3647
aa5s
3657
3668
3664
ease
3444
7665
2344

PALE-V7

DFIC
OSEF
OST
bYI
EAE
EAETPL
EARETF2
END
ENOCHK
ENDCKI
ENOCL
ENDC2
EXEC
EXECH
FACT
FACTOR
FCHANG
FCHRET
FIT
FRCFCT
FRCNVI
FRONYT
FRON4
FRON2
FREXIT
FREXTL
FRNCTR
FRAIMF
FRTEMF
GAC
HOBLOK
HDRBLE
HISET
HUNCRS
INPL
INTCIF
INTOF
INTCIN
INTONL
KL?
K246@
K34@

“Ke

LINE
LMASS
LOAL
LOCMAS
LOCTIM
LOSETI
LOWSET
LPOINT
LSR
LSTMAS
MASCTR
MASOIF

Pos
Qasr?
P7445
74ar
aaet
Q154
@152
2647
2475
aaéa
=14z
z127
tea
abet
4574
aaéz
2661
2664
4514
S712
GHes
Sé4a
S64
S657
Sra.
S7@5
SPL
or22
5714
Sz2z
S565
aa64
2233
S72
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PALEY? PAGE 4

ROINTS

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?GET NO. POINTS FER PASS.
7GET MAX. RUN TIME

“PRINT "“TITLE:"

“ENABLE TTY READ
fREAD TITLE

fPRINT "2?"

7SET PLOT FACTOR
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CENABLE TTY READ
7INITIALIZE PLOTTER.

7TURN MS INTERFACE ON.


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EPA-660/2-74-004
January 1974
SPECIFIC ION MASS SPECTROMETRIC
DETECTION FOR GAS CHROMATOGRAPHIC

PESTICIDE ANALYSIS

By

Maynard B, Neher and James R. Hoyland

Grant No. R~800909
Project 16ADN 28
Program Element 1B1027

Project Officer

Dr. John M. McGuire
Chromatography & Mass Spectrometry Section
Southeast Environmental Research Laboratory

Athens, Georgia 30601

Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D. C. 20460

For sale by the Superintendent of Documents, U.8. Government Printing Office, Washington, D.C. 20402 - Price $1.65


?/SIMPLT.

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DLDSH..

DADSM,

DPS2SM,

CLL

PALEY? PAGE 18-1

ERETFS
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DLDSM

STORE
“RESTOR AC
“TNE

@STORE MSH

“GET LSH TO AC

PCOMPLIMENT AC SET LINK TO ZERO
eIF AC WAS ZERO

“GET LINK BIT

@ADD TO MSH

eCOMPLIMENT

?CLEAR AC. Me
GET ADDRESS

“UPDATE RETURN

“DOUBLE ADD TO A CLEAR AC. Me

CLOSM
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DADSM

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DADS

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“STORE AC

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“STORE

UPDATE RETURN

“SWAP MG. AC
CLSHCLI+LSHE ES
PUT IN Me
?GET CARRY BIT
?MSH ADDRESS

@MSHCLIFMSHC 2D
“DONE

ACHE?

?NG - NORMAL RETURN

“YES - CHECK MG

“Mesa?

eVES ~ UPDATE RETURN FOR SKIF
@RESTORE


/SYMSON PAGE 1a~4

4344 TMs SIGN?
Sear TMP F GIVIDE
PGUOTIENT IN AC-M@ CN RETURN. MSH IM AC
aqaea DIvId, &
goaa OBIVig,
GGG GIVIs, &@
“ERE MULTIPLY ROUTINE
PMULTIPLIES GOUBLE F
“BY SINGLE PRECISION MULT
ePRECISION PRODUCT IN AC
PCALLING SEGUENCE:

IN RMULTIPLICANS IN 4

é IMs CMLL T 3
? TMULTIFLIER Af

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63


/SYMSCN PALS-VP PAGE S-=

@2573 2067 18Z LOCTIM INCREMENT POINTER: - -
@2574 3467 DCA I LOCTIM /REFEAT FOR NEXT MASS
92575 2466 1sz NTIME INCREMENT COUNTER
G2576 S372 IMF SET2 “OO NEXT CINE
@2577 S743 UMP I TIMSET

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266@ PAGE


“SIMPLT. : PALS-YF PRGE -2

ee
2486 PAGE


Calculate No. of words
to write (multiply
No. of blocks by 200

(OCTAL)
I
‘Subroutine for recording Negate and store
data blocks count for zero fill

Write buffer to
mass storage device

No
Done?
Yes
Fape> Yes
Backspace No
done?
Yes
Fill buffer
with zeroes

Turn MS interface on.

Subroutine for recording
header blocks

Write header block

Tum MS interface on

FIGURE 10. FLOW CHART FOR MASS-STORAGE-DATA-RECORDING ROUTINE

23


The initial program version plotted data on line as discrete points.
Data thus presented was quite noisy. To decrease the noise level, a
least-squires smoothing routine was added to the program. This
routine uses the technique of Savitzky and Golay, (5) in which smooth-
ing is obtained by multiplying successive values by a set of smoothing
factors, and dividing the sum of the products by a normalizing factor.
A flow chart for this smoothing routine is shown in Figure 8.

Data Processing and Recording. The program uses one core page to record
the title of the run and the data acquisition parameters. At the start

of the run, this page is written onto the mass storage device as a
header block. Five core pages of memory are used as a buffer for
recording data. When the buffer is full, the data are written on the
mass storage device, the buffer is filled with zeros, and data are then
entered starting over at the beginning of the buffer. A flow chart for
the data processing and recording routine is shown in Figure 9, (The
program is independent of the mass storage device and will work on
either disk or tape systems). The program checks to see that there is
room at the end of the buffer for an inter-buffer flag. If there is
enough room when a change of data recording parameters is signalled by
the keyboard interrupt routine, a two-word inter-buffer record mark
(7070 0000) is entered in the buffer. The buffer is then written on
the mass storage device, and a new header block is recorded to indicate
data acquisition parameters. If there is not enough room, the inter-
buffer record is started at the beginning of the next block, so that
the end-of-record flag will always be at the location for the start of
a data set. When the run is terminated, a two-word end-of-file record
mark (7171 0000) is entered in the buffer, the buffer is written out on
the mass storage device, and the file is closed and catalogued in the
system directory.

19


“SIMPLT. . PRLE-VP PAGE 14

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Legend

209 DDD \
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Ss 292 Parathion ‘|

292]
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243 it

Carrier Gas:Methane, 30 ml/min
Column Temperature :170-250°C,
10°C/min
Column: 4 ft. x 2 mm, glass,
2-1/2 percent DEXSIL
300 on Supelcoport

243

Real Time Plot Reconstructed Plot
FIGURE 15. SIM PLOTS OF CL GC/MS OF PESTICIDE MIXTURE, 1 ng EACH

31


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PALS-¥F PAGE 7-2

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7NG. DISK. RETURN
“YES. GET BACKSPACE FLAG

“NC. WAIT.
“VES. RETURN

TEXT416, TEXT “CLOSE ERROR! /


/SIMPLT.

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PAGE 16-2


fSYMSCN PALE-VP PAGE 16-1

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Qa5r4? S275 JMF SETERR

@5756 7575 DCM “NEGATE.

@5751 445 DAD “SUBTRACT PREVIOUS
@5752 3254 TOTAL ¢ VALUE,

@5752 7575 ocM “NEGATE TO MAKE POSITIVE
Q5754 7445 Muy “MULTIPLY BY FRACTIONAL
@5?55 @445 SFACT ¢ MASS.

@5756 7424 ACHC “PUT RESULT IN MG
B575? 744s DAD “ADD IN LOWER MASS
@5768 3354 TOTAL ¢ VALUE

85761 7445 SETCe, DST &D. PF. STORE

Q57é62 G00G RODADD, @

Q5763 7é2z4 CAM :

O5764 2072 Isz MNMASS = “DONE?

a57é5 7416 SKF

Q5766 S3zrzF JMF NORRET

Q@576? 2362 1sZ ROCADD “INCREMENT POINTER:
Q577G 2362 1sz RODADD

Q5r7741 2624 : 1sz ADMASL

Q@5772 5326 aa IMF SETCAL+2

@S773 2324 NORRET, ISé SETCAL NORMAL RETURN

a5774 2324 1sZ SETCAL

Q5775 Sr2@¢4 SETERR, JMF 1 SETCAL


Ez

Print file
name

E
Enter

file name

I

Search
directory

Print "7?"|

Search file;
get minimum
and maximum

values
i

Set baseline

correction

and scale
factor

Set up for

first mass

Plot mass
number

Plot mass
curve
(smoothed plot)

Print EXIT
"Change
pen"

Yes CR? No Advance plotter
: ‘3 inches

Return plotter
to overlay plots

FIGURE 12. FLOW CHART FOR OFF-LINE PLOTTING PROGRAM

25


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IMF
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NP TSS
APRSCe
SPCADL
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SMTH®
MIN

YTOBPL-2

CINORM
YTORPL
ABSYRG

YTOEPL
YTOBPL
FRSFLG

+

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PLTSTP+S
BF2ETZ

P2eTs

SPCADD
SPCADD
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tf

INCLFE
EREFR2

BAF PAGE 6

C#ROF PTS/BLOCK

CSUBTRACT MINIMUM

¢Y VALUE RELATIVE TQ CURRENT ORIGIN
CFIRST TIME?

ePLOT IT


Baseline noise due to column bleed is a significant problem in gas
chromatography, particularly in programmed temperature operation. It is
usually corrected by dual column operation, bucking one against

the other (i.e. by baseline subtraction). For combined gc/ms, a single
column technique, this solution is not feasible. The System 150 programs
provide a background subtraction capability for display of individual
spectra, but have no way of suppression or subtraction of the baseline

in reconstructed gas chromatograms. Since baseline suppression is
necessary for maximum sensitivity this is a serious shortcoming of the

standard System 150 programs.

Further, the ions of interest in a gc/ms run change with the progress of
the run. The standard System 150 programs provide the capability of
monitoring only a few ions, but monitors the same set of ions during the
entire run, Since all ions of interest must be monitored all the time,
this reduces the percentage of the time that can be spent on each, thus

reducing the theoretical signal-to-noise enhancement of the SIM technique. .


“SYMSCN . PALS-VF PAGE 16-2

O5r7é 2252 ACALIE. CALIB
O5?77? 2264 PRSETI, PRESET
$


/SIMPLT.

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64143 6632
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46145 GGaG
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*67
APENUP,
APENDN,
ACRON,
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ACHTRT,
ACHLCU,
ACHRCD,

ADIMOVE,

*41 37

READX,
WAITE:
ASTMSP,
PIMASC,
AFLOTH,
cOMASS,

P2z7,
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NSMOCT,
SMTHX,

PALS-VP

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415
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a
a
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DFSZSM >

IFNZRO ERE <¢

SWAB=7434
DST=7445
DLD=7662
DAD=7442

PAGE 2-2.


SECTION II

RECOMMENDATIONS

The debugged Selected Ion Monitoring programs should be made available
to users of Finnigan quadrupole mass spectrometers equipped with System
150 data systems.


?SIMPLT. PALE-V? PAGE 16-1

as466 7500 SMA

as467 5275 MP +4

a547@ 7444 c1A

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a5472 41356 TAD SIGN

O5473 3266 DCA MLFELR

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45475 @ooa F54T2, @ GET POINT
5476 7456 SNA /DOUBLE PRECISION?
asd?77 5264 MF +5 °
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5564 4357 TAD ROTAT

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g5543 7575 pen /COMPLIMENT
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5521 2275 ISz P5472 /ADDRESSES
5522 2275 1SZ PS4TS

5523 2355 ISZ PS4T4 9 “DCINE?

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5527 3235 DCA +6

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5534 5562 TOTAL

@5532 4762 UMS I NORMLS

5532 5564 COEFSM fCOEFSM CONTAINS ADDRESS
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5535 aaea 8

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PALS-¥?7 PAGE 2
éSIMPLT

“THIS PROGRAM PREPARES NORMALIZED PLOTS FROM DATA FILES
@CREATED BY THE "SIM" SCAN FROGRAM. IT USES THE STANDARD
“SYSTEM 45@ PROGRAMS. THIS VERSION REQUIRES A FDPS/E. OR

“S/M BUT INCORPORATES EAE SIMULATOR ROUTINES FOR

/SYSTEMS WITHOUT THE KES-E EXTENDED ARITHMETIC

fELEMENT, EAE. FOR SYSTEMS WITH ERE, DEFINE EAE=1 TO
“ASSEMBLE A PROGRAM USING THE ERE

?

“PLIST CONTROLS LISTING GF THE S$. 1. PLOTTER ROUTINES

“IF NOT DEFINED ¢ GR SET EQUAL TO ZERC > THE FLOTTER ROUTINES

CARE NOT LISTED. IF SET NCINZERCG. THE PLOTTER ROUTINES ARE LISTED
?

IFNDEF PLIST <PLIST=@>
é

NGASP rat
LINE=6224-
SWP=?7524
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PALS-V7 PAGE 44

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CUPDATE REURN

“LOW ORDER FRODUCT
7TO MG
7HIGH ORDER PORDUCT

7UNSIGNED S.F. DIVIDE
?STORE ‘MSH *
7GET LSH
?STORE
7GET DI¥ISGR ADDRESS

CACTUAL DIVISOR
7COMPLIMENT
?STORE

@CHECK FOR OVERLOW
COVERFLOW


“SIMPLT.

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FALE-VF PAGE S-L
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TEXTS,

PALE-VF

TEST DUPLICATE FILE NAME!“

TEXT “NG. POINTS: +

TEXT “RUN TIME: ¢

TEXT “ANCTHER SET?“

TEXT “SCALE FACTOR: ¢

“SUBROUTINE TO SET POINTERS FOR SETCAL
“SUBROUTINE TO INITIALIZE FLOTTER.

PLOTIN,

a

IOF

NL???? fACH-41

IMs I PLOTT 7SET NEW ORIGIN

PAGE

1


AS9MSCN PALSY? FAGE ?

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a
a
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#3080

SUBROUTINE FOR INITIALIZING FOINTERS PRIOR TO CALL
“MASSET AND TIMSET.

8600 FTES. a

1923 TAD AGMASS
azeg2 34147 OCA TACMAS 4ST MASS STORAGE Loc
G3gas 1626 TAD ACTIME
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428066 34125 DCA TMASS “Loc, FOR NO. MASSES
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43662 2502 AMSSET. MASSET
63063 3547 AGUERY, QUERY


point being calculated, and 1 and 2 are the mass/voltage points bracket-
ing the point being calculated. If a mass that falls outside the range
of the calibration file is entered, an error message is given, and the

program waits for an acceptable set of masses.

A flow chart for the initialization program is given in Figure 2. Flow

charts for subroutines used during initialization are given in Figures 3-5.

Mass Spectrometer Scan Control, The mass spectrometer scan is controlled
by the computer using the normal mass spectrometer interface and controls.
However, to optimize data handling and storage, the selected masses are
monitored sequentially. The integration time for each peak must be
selected such that the integrator does not saturate in the time selected.
To avoid storing many small numbers, a number of sets of masses are
scanned and the intensities for each summed using double precision
addition.

A keyboard monitor allows the operator to change acquisition parameters
during a run. If a change is requested, a marker is inserted in the mass
storage record, and a new header block is written showing the new para-
meters before data recording is reinitiated. A flow chart for the scan

control is shown in Figure 6.

On-Line Data Presentation. The data acquisition program provides for
on-line plotting of the intensity of the first mass monitored. (Because
the plotter is relatively slow, there is not time to plot all the peaks.
in real time without placing rather severe restrictions on the combinat-
ion of parameters for data acquisition). The first mass in the list is
the one that is plotted; however, the entries do not need to be in
increasing mass order, so any mass can be plotted in real time. A flow
chart for the on-line data presentation portion of the program is given

in Figure 7.

15


/SYMSCN

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TEXT?
26
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PALS-¥P PAGE 4-402,

DONE

SINTRF
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?VES. DONE WITH SEARCH. ‘2. .
“ACSA? CMASSDCALIBRATION mA
“NG. INTERPOLATE. :
#WES., CHECK NEXT POINT.
@INCREMENT POINTER

°GET NEXT CALIBRATION PERK.
fZERO?

eNG. PROCEED

“PRINT "MASS GUTSIDE
“CALIBRATICN RANGE. "

?FIRST POINT?
?VES. ERROR.
eRC=-4

“POINTER TQ PREVIQUS POINT.
“PREVIQUS CALIBRATION MASS
“SUBTRACT FROM MASS TO

“BE CALIBRATED AND STORE
fPREYIOUS CALIBRATICN MASS.
@NEGATE

“ACD LAST CALIBRATION MASS

“LAST POINT COUNTER

“START CF ROD CALIBRATION F
@ADDRESS OF PREVIQUS SETTING
fACS-2

CPREVICUS ROD SETTING ADDR.

“STORE FOR USE LATER.
7b. PF. LOAD

fPREVIGUS ROD SETTING
7b. PP. COMPLEMENT

7D. PL AGG LAST

fROD SETTING

@MULTIFLY BY
“INTERPOLATION DIFFERENCE
CMULTIPLY OVERFLODL
(DIVIDE By DIFFERENCE

7IN MASSES.

ADD PREVIQUS SETTING
“CALIBRATION VALUE IN AC-MG@

“GET LAST VALUE POINTER.

“ADDRESS OF VALUE.

“STORE.

7D. P. LOAD LAST VALUE.
@CALIBRATION ¥YALUE NOW IN
“INC. FOR NORMAL RETURN


“SYMSCN- PALES-V? PAGE 5-2

92585 3666 DCA LOCMAS OF MASS TABLE.
82506 4437 vMsS I APL @PRINT "MASSCES:"
62507 3224 TEXT4

62516 G@85 5

92511 16056 TAD ATTRDI

@2512 352? CCA I TTRD

92543 4457 gMs 1 DSPF

2514 4427 gms I AINFL CINFUT MASSCES?
92545 3527 DCA I TTRD “DISABLE TTY READ
2516 4424 NXTMAS, JMS I ADEG “RETURN OCTAL NUMBER
@251? 5335 uMP LSTMAS END OF LINE.

$2526 7008 NOP

$2521 2466 bcA I LOCMAS /STORE NUMBER

62522 2066 Isz LOCMAS /INCREMENT FOINTER
62523 1422 TAD I ACEQ4 “TERMINATOR,

G2524 1078 TAD M56

62525 7646 S2A CLA @DECIMAL POINT?
2526 5334 oMF +3 “NG. ASSUME INTEGER
G2527? 4463 IMS 1 FRCNVI ¢GET CCTAL FRACTION.
$2520 5346 JMP MERROR ERROR RETURN

B2534 3466 CCA I LOCMAS /STORE FRACTION.
@2532 2666 Isz LOCMAS INCREMENT POINTER.
G2533 2676 Isz NMASS “INCREMENT COUNTER,
2534 5316 IMP NXTMAS.

62535 1076 LSTMAS., TAD NMASS

2536 23523 DCA I TMASS

82537 S7a2 IMP I MASSET “NORMAL RETURN.
9254@ 2302 MERROR, 152 MASSET

92544 2302 1sz MASSET

$2542 5S7a2 oMP I MASSET

7SUBROUTINE TO READ INTEGRATION TIMES.
2543 G08 TIMSET, G

G2544 4427 gMS I APL ?PRINT “INTEG. TIME:"
62545 3234 TEXTS

@2546 oaa7 ?

@2547 7346 TIMST1, NL?777 PACSH4

62556 1126 TAD TADTIM

92554 3067 oCA LocTim

92552 41523 TAD I TMASS

@2552 7644 cIA NEGATE

92554 34140 DCA NTIME

62555 1956 TAD ATTRDI

G2556 3527 DCA 1 TTRD /ENABLE TTY READ

2557 4457 JMS I DSPF

G2560 4427 JMS I AINFL READ INTEGRATION TIME
62561 3527 DCA I TTRD /DISABLE TTY READ
@2562 4424 NXTIME, JMS I ADEO ?GET INTEGRATICN TIMES
92563 7600 NOF

92564 5372 oMP SET2

62565 2467 1Sz LOCTIM /INCREMENT POINTER
B2566 32467 DCA I LOCTIM /STORE INTEGRATION TIME
2567. 2168 1SZ NTIME INCREMENT COUNTER
2570” 5362 ome NSTIME /GET NEXT TIME

62571 5743 JMP 1 TIMSET /FINISHED

2572 1467 SET2, TAD I LOCTIM /GET TIME


fERE DEFINITION. PALE-¥e FAGE 1

7ERE CEFINITIOCN.
¢
G61 EAE=14


3. Integration Time. The integration time is specified,
in milliseconds (max of 4096). As many integration
times can be entered as masses. However, if fewer
integration times are entered than masses, the last
time entered is used for the rest of the masses.

(All masses can be monitored at the same integration
time by entering only a single integration time).

4. Number of Sets of Masses. To permit rapid change of
conditions, up to three sets of masses and integration
times can be specified at the start of the run.

5. Number of Points to Scan For Each Mass. The specified
number of values for each mass are summed and entered as
a single value in the file of recorded data. This permits
the equivalent of long integration times and frequent
data sampling so that real data fluctuations are not
missed,

6. Title of Run. Room exists in the record for a des-
criptive title of up to 40 alphanumeric characters,

7. Maximum Time of the Run in Minutes. When the specified
time has elapsed, the run is terminated automatically.
However, the run can be terminated earlier if desired
by entering E(CR) on the teletype. Control-L (depress-
ing both the control key and L) aborts the run, i.e.,
terminates it without entering the file in the system
directory.

8. Data File Name. This is the name (six characters
or less) by which the file is catalogued on the
system device.

In the initialization program, the calibration file data are packed into
the proper format to set rod voltages, and the rod voltage settings are
calculated for each set of masses entered. A linear interpolation is used
for the calculation: V, = Vy + (M_-My) % (V2-V1)/(Mp-M,) where c is the

10


“SYMSCN

G2735
Q27z6
Q2737
G2748
G2r44
g2rd2
B2743
g2r44
B2745
G27r46
g2747
92756

g2754
62752
G2752
G2754
G2755
82756
g2757
62766
62761
a2762
G2763
B2764
G2765
G2766
g2767
@2776
G2774
g2772
B2773
B2774

P7485
@ia4
rrad
1626
3124
1374
7456
5346
PP2d
1633
34122
S266

1268
2755
Sr54
2547
2542
54132
2445
2464
3457
P4733
7564
ré6ri
PPP?
goG6
eaa4
6a67
8086
686G
5122
S544

MCHAE,

MCHAP,

¢ CHANGE
TCHANG,

ATIMS4.
TIMSTI,
CRLF,
ANFNTS,
APLTF4,
APLTFC,
MEE,
MCNTRL.
MESS,
MTEE,
MEN,
MEM,
MEFF,
SDIFF,
STORE,
ATTYT,
TELRD,

Muy
Psi
MGAR
TAD
DCA
TAD
SNA
wMP
M@AC
TAD
DCA
oMP

PALE-¥? PAGE 6-2

“PUT ANSWER IN AC.
ADTIME ¢START OF 1ST TIME ARRAY.
TADTIM ¢START OF THIS SET OF TIMES.
SDIFF
“SET NO. >4?
MCHA “NG.
“GET OFFSET FROM MG.
AMASSL “START CF MASS TABLE
THASS “Loc, OF NQ. MASSES.
MCHAL

INTEGRATION TIMES

TAD
DCA I
vMP 1
TIMST4
TIMSET
TTYCR
NPNTSL
PLTFCL
PLTFCT
-385

NCHRET

TIMSTI ¢CHANGE RETURN ADD.
ATIMS4

7214-323
?323-324
7324-316
7316-315
7345-387


FIGURES

No. Page
1 General Program Flow Chart 9
2 Flow Chart for Program Initialization 12
3 Flow Chart for Calibration-File-Packing Subroutine 13
4 Flow Chart for Subroutine for Imputting Masses, Integration

Times, Total Run Time and Number of Points to Sum 14
5 Flow Chart for Rod-Voltage-Setting Subroutine 15
6 Flow Chart for Mass~Spectrometer~Scan Routine 17
7 Flow Chart for On-Line Data Plotting Routine 19
8 Flow Chart for Data-Buffer-Processing Routines 21
9 Flow Chart for Mass-Storage-Data-Recording Routine 22
10 Flow Chart for Smoothing Routine 23
11 Flow Chart for Keyboard Monitor 25
12. Flow Chart for Off-Line Plotting Program 27
13. Electron Impact and Chemical Ionization Mass Spectra of

ps p'-DDT ’ 31
14 SIM Plots of Single Pesticides 32
15 SIM Plots of Pesticide Mixture 34

iv


/S4MSCN

PALE-¥?P PAGE 15

?THE REST GF THE EAE SIMULATOR ROUTINES

IFZERO ERE <

#5645
MUYSH,

MP4,

MP3,

MPS) |
THIR:
DYISM,

DYE,

a

CLA
SWF
DCA
TAC
CCA
TAC

CLL

OCA

Isz
DCA
TAD
OCA
TAD
RAF
bCA
TAC
SNL
JMP
CLL
TAG
RAR
DCA
Isz
UMP
TAD
RAR
SWF
TAD
uMF
@

(3)
Pred
a
DCA
SWF
DCA
TAD
DCA
TAD
ClA
DCA
CLL
TAD

TAD

Isz
S2L
uMP
TAD
DCA
JMP
TAD

I

CLA

EAETPL
Muyse
EAETFS
EAETF2
EAETF2
MUyYSM
MPS
THIF:
MPS
EAETFL

EAETFEL
MPS

.t

tet

EAETF2

MPS
MPS
MP4
EAETFL

MPS
MuYSM

EAETPA

EAETP2
OVISM

DIVSOR
DIVSOR

DIVSOR
DI¥SOR
EAETF4
DYISM

DVISM
MDVis

DIVCNT

pyv2
EAETF 4.

PSINGLE PRECISION UNSIGNED MULF
“GET MULTIPLIER

“STORE

“GET ADDRESS OF MULT.

“MULTIFLICANE

UPDATE REURN

“LOW ORDER PRODUCT
“To Me
“HIGH GROER PORCUCT

“UNSIGNED S. FL DIVIDE
“STORE MSH

“GET LSH

“STORE

“GET DIVISOR ADDRESS

ACTUAL DIVISOR

“COMPLIMENT
?STORE

?CHECK FOR OVERLOW
COVERFLOW


READ
KEYBOARD.

ERROR VES

CHANGE MASS &
TIME SET

READ
KEYBOARD

<

NO
[enron} es

GET NEw
TIME(S)

(Subroutine
TIMSET)

|__

READ
KEYBOARD

|_—__] ves >

READ
KEYBOARD

Yes

END OF RUN

INSERT E-0-F
IN RECORD.

(Subroutine END CHK)

CATALOG FILE

READ
KEYBOARD

GET NEW
MASS(ES)
{Subroutine
MASSET)

|

READ
KEYBOARD

NO

A

CHANGE
NUMBER OF

CHANGE PLOT
SCALE FACTOR
(Subroutine PLTFCT)
[_serunn |
FIGURE 11. FLOW CHART FOR KEYBOARD MONITOR

24


?SYMSCN PALE-¥? PAGE 14-1

@4464 2114 Isz SETFLG ¢SET FLAG.

4465 6374 WAITI, SKMO 7M. S. READY FOR GUTPUT?
64466 7416 SKP “VES,

4467 5265 JMP te 7NG. WAIT LONGER,
G4476 7166 CLL 7LINK MUST BE CLEARED.
@4474 6372 Misa COUTFUT CER.

G4472 566 IMP I CHKSET RETURN.

4473 6371 WAIT2, SKMO 7MS READY FOR GUTFLUT?
o4474 7418 SKF 7WES,

64475 S2rz uMF 272 7NC WAIT LONGER.

64476 6372 usc COUTFUT CBR.

ad477 7344 NL? 776 fACS-2

@45a@ 1844 TAD ASETT RESET VOLTAGE ARRAY
@45@1 3644 OCA ASETT “ADDRESS.

@4502 2135 1Sz WTFLAG BUMP FLAG

G@4563 704 NOF

64544 5765 JMF I +t

64565 2414 MSLOOF

64506 aoaa PTBUFG, @
B45G7 @00@ PTBUFL, @
?SAVITZKY-GOLAY SMOCTHING ROUTINE.
?THIS VERSION SMOCTHS 14 POINTS.
7FIRST FOINT TO SMOCTH IN CALL+1.
7SMOOTHED POINT RETURNED IN AC, SINGLE PRECISION.

@4514@ aoea FIT. a

@4544 1746 TAD I FIT

44542 3372 CCA SMADD “STARTING ADDRESS.
64543 2318 Isz FIT

$4544 4371 TAD NSMCCT

64515 7a41 ciA .

44516 3372 DCA _ CTR CSET UP POINT COUNTER.
44547 4375 TAD AFACT

64528 3374 DCA FACT

@4521 7621 cAM

64522 7445 DST

94523 3354 « TOTAL

64524 4773 SMLOOF.s TAD I SMADD

64525 7424 ACME 7INTENSITY TO MG.
@4526 1274 TAD FACT

G4527 3334 DCA SML1

G@453a 4475 gms 1 MULTI (CALL MULTIPLY ROUTINE.
@4531 @@08 SML1. a

64532 7402 HLT

Q4533 7443 DAD

G4534 3354 TOTAL

G4535 7445 DST

@4536 0 3354 TOTAL

Q4537 7624 CAM

S454 2373 ISZ . SMADL “INCREMENT ADDRESSES.
84544 2374 IsZ 4 \ FACT :

44542 2372 ISZ CTR “DONE?

84543 S324 JMF SMLOOF “NG.

B4544 A374 TAD FACT

64545 3354 DCA SMLe

@4546 7665 OLD “VES. GET TOTAL


“SYMSCEN PRALE-VP PAGE 9-1

@3y464 3212 TEATLS
@s462 aGar ?
Bz463 4457 gms 1 OSPF a
G@s464 4427 PLTFCA, IMS 1 AINFL “READ SCALE FACTOR
Bz465 4424 gms I AGEO PDECIMAL-OCTAL CONYERT
Bx466 4442 gms I AGUES © ERROR
Q34er 3264 JMF PLTFCL ¢TRY AGAIN
Q247@ 3062 OCA FACTOR
B34741 5657 uMF I PLIFCT
“SPACE FILL PRINT BUFFER
G@3472 O66 SPF, a
Bz472 P2aG CLA
63474 1206 TAD SPFL “RET COUNT
@3475 3344 . DCA SPFS “TEMP STORAGE
@3476 1632 TAD ALINE
Q@s477 3367 DGA SPFZ “STORAGE ACR
S258 4216 SPF, TAC SPF4 fSPACE FILL
B3501 3747 DCA I SPF2 “STORE
@3502 23407 Isz SPF2 “UPDATE STR ADDR
G3582 2344 Isz SPFS “FINISHED?
@z544 S530a IMP SPF “Na
G3585 Ser2 UMP I SPF “YES-RETURN
B2596 P776G SPF1, 7Prée 7-24 OCTAL

6356? 8606 SPF2, a
3516 4644 SPF4, 4846
G2511 G06 SPFS, 6
SUBROUTINE TO WRITE DATA RECORDS.
G@2512 4600 WRIDAT. @

2513 4ar7di2 TAD I WRTDAT GET NG. BLOCKS.
G@z514 23412 Isz WRTGAT

3515 424 ACNC “PUT IN MG

@3516 7465 Muy PMULTIPLY BY aed.
@3517? 2546 P2e4

$2526 7436 Sé2b “ERROR?

G@2521 7402 HLT

@3522 7524 SWF “PRODUCT TO AC
@z523 3525 OCA WRTNUM

Ox524 4225 TAD WETNUM

$2525 ?7e44 cIiA

Gz526 2164 DCA NWORDS COUNT F@OF PZER FILL
@352? 18268 TAG ABU EG “SET POINTER FOR
93530 2434 DCA AMPPTR “FOR 2ROFIL

@3531 4436 ous I AINTOF

G2532 6664 IGN

S353 4532 ms I WRITERS

$3534 G66 a

2535 @66G WRTNUM, @ fNO. WORDS TO WRITE
G@3526 6600 BUFG “ADDRESS

@3537 4868 a “DONE FLAG

Gz540 4522 JMS 1 WAITS

62541 72668 CLA

Bz542 4524 gms 1 TCHCKI

G2543 6662 IOF

G@3544 4536 ous 1 ZROFLI ¢ZERO-FILL BUFFER

@2545 Sri2 oMF I WRTDAT


Reset 2 sec,
‘counter

L______—7

‘Set MS interface
(Subroutine MSSET)

T

Plot point
(Subroutine CHKSET)

Oo

Yes

i

‘Add to SH
buffer value

Tncremeat
MSH value

(Get address of intensity
for firs mass
L
‘Store pointer
for plotter
I
Tnerement buffer
counter

Yes No

‘Get primary

buffer pototer

Write buffer L

to mas storage Tnerement to
device start of next
(Subroutine WRTFIL) set of points

Tos Tos

FIGURE 6. (continued). FLOW CHART FOR .MASS-SPECTROMETER-SCAN ROUTINE

17


“ERE DEFINITION. PALES -V7 PAGE 1
“ERE DEFINITION.

e

8001 EAE=4


“SYMSCN : FALS-VP PAGE 7-41

Q@seé64 2543 ATMSET, TIMSET

Gsa65 828 Fea. 2a

Ssaée PP?5 MEST. =
“SUBROUTINE TO WRITE,E-O-R FLAG ON DISK OR TAFE.
“SUBROUTINE TO ZERQ-FILL BUFFER

Q3667 G68 2ROFIL. &

B2ar7G F434 ER4- bCA I AMPPTR

Bzeari 20rd Isz AMPPTR

Qzar2 2464 Ise NWORDS “DONE?
G2ars Sera . vMF ER4 NC.
Sard 5667 IMP I ZROFIL

“SUBROUTINE TO END RECORDS.
G3875 8668 ENDCHE, @

G@Ea7é FSET DCA NBLOCK /ZERO BLOCK COUNTER.
Bzer?y 1925 TAR ADSTOR natal BUFFER ADDRESS TO
G2160 334 CCA AMPETR START OF CURRENT SET
S314 1634 TAD AMPFTR OF MASSES.
G12 a4 TAD Méaaa AMPLITUDE BUFFER START.
G@za@= 4341 ENDC41, TAD Mead
B2184 2335 1s2 NELOCK INCREMENT BLOCK COUNTER.
B3105 P5de@ SMA S2A “DONE?
G3166 Szaz IMP ENGCL eNO. DO MORE. a
S210? Prs4ea SZA CLA “YES. ANY ROOM LEFT IN Blac
@3444 3227 UMP ENDC2 “VES.
3114 41235 TAD NELOCKE ¢NO
G2412 41344 TAD M5
$3112 7454 SNA #5 BLOCKS?
Qiii4 S247 JMP +3 oVES,
34415 2235 1S2 NBLOCK NO. BUMP BLOCK COUNTER
@34146 Sze? uMP ENDC2
G44? 4534 uMs I WRTFIL ¢WRITE GUT FILE
@3120 @aa5 3
Q@z121 16246 TAD ABUF@ “RESET POINTER
@s422 zaz4 DCR AMPPTR
Ox123 Pred NLeeat fACEL
G3424 3253 CCA NBLOCK SET BLOCK COUNTER FOR WRITE
@2125 Psdd NLFFPS6 eACS-2
@sizé 34104 DCA NWORDS ONLY 2 WORDS TO ZERC QUT.
@st27 2634 ENDCe, I82 AMPPTR
B2136 1675 TAD I ENDCHE /GET E-O-R CHARACTER.
G@i434 3434 DCA I AMPPTR “STORE E-O-F CHAR.
@s4132 4534 ams I WRTFIL
Gi435 G60 NELOCK. @&
B2iz4 1626 TAL ABUFa@
G2135 2Hr4 OCR AMPPTR RESET BUFFER LOCATION
3436 2275 1sz ENOCHE
@i437 SéPs IMP I ENDCHK
O314@ 777s MS. -5
Qi144 Parr Mead, ~264
$3142 2608 Ménom, -6ane
?
$2143 8604 WTEATA, &
Gt144 447 ms 1 APL @PRINT "DATA"
gi4145 3241 TEATZ

Bi146 eae 2


Entry

Subroutine
FIT

Get and store
first point address

Set counter

Clear total

Get data point

Multiply by factor

Add product to total

Increment pointers
and counter

D. P. load total

Divide by
normalizing factor

Quotient <O?

set =O

Set = 1700 No

Return

EIGURE 8, FLOW CHART FOR SMOOTHING ROUTINE

20


?SIMPLT.

B2354
ag255
B2356
a2287
a2z6g
as364
B2362
a2362
agze4
ae365

S751
2668
2732
aang
1zé4
4543
r2eq
SPs?
6302
3146

2460

22000,
AXMSCL,
TRNON,

PLOTON,
APRSOL.
fe

PAGE

IMF I
2080
YMSCLE
a

TAL:
gMs I
CLA
IMF I
6za2
PRESRC

PRILG-Y7

SETMSPF:

PLOTCN
APLOTH

TRINUIN

PAGE


SSUMSCN FALE-V? PAGE 2-4

g2066 4762 RESCAN, JMS I DCONTI /SET STORAGE POINTERS

g2ne7 1626 TAD ABU Ee “BUFFER START ADDRESS.
g2a7a s3az4 DCA AMPPTR

B2a7i 1275 TAD M1285 “BUFFER LENGTH

genre Ziad OCA NWORDS COUNTER FOR ZEROFIL
@za7z 4526 gus 1 2ROFLI “ZERO-FILL BUFFER.
w2u74 1626 BUFSET, TAD ABLIFG

aza75 3025 DCA ADSTCR “SET BUFFER POINTER.
azar7e igre TAD MLEN

B2077 DCA BUFENL: -

a2ig@ 4424 uMs 1 AINTON TURN MS INTERFACE ON.
g2ig1 1874 CYCLE1, TAD MiNUM “NG. POINTS PER MASS.
B2162 s264 CCA LFOINT

42102 41625 CYCLEe. TAD ASTOR “SET BUFFER

g2iad+ 2ar4 CCA AMPPTR “POINTER:

2195 1522 TAD I TMASS “NUMBER OF MASSES
2196 Pada clA “NEGATE

G2197 zard DCA MASCTR 8 ¢STORE

M@2iie 41126 TAD TADTIM “GET AND STORE

M2144 zade CCA ATIME “TIME ADDRESS

M2ii2e 44423 TAD RODSTT GET AND STORE

M2143 264d CCA ASETT “SETTING ADDRESS
G@2idd i446 MSLOOF, TAD I ATIME “GET INTEGRATION TIME-
2115 1126 TAC TRTIME ADD 1 SEC. COUNTER
2116 3126 DCA TRTIME

G@24i7 1126 TAD TRTIME

2126 7514 SPA “GE. a?

@2124 S227 uMP MSET “Na. CONTINUE.

HWai22 2124 Isz TOTIME “VES. INCREMENT RUN TIME CO
“@z1z% 7440 SKF “TIME LIMIT EXCEEDED?
G@2424 S445 UMP I ARGCHRE WES. EXIT.

@2125 41374 TAD M175@ “NG. RESET 4 SEC. COUNTER
Gai26 3126 DCA TRTIME

G2i27 4765 MSET- ams 1 MSSETI SET INTERFACE

B2124 4775 JMS 1 CHKSTI

G@2134 idz4 TAG I AMPPTRE ADD TO STORED VALUE
G21z2 34234 © CCA I AMPPTR “AND STORE.

G@21zz% 2634 ~ Isz AMPPTR INCREMENT POINTER TO MSH.
G@21z4 7436 S2-_ fOVERFLOW?

G2125 2454 IsZ 1 AMPPTR “YES

@2iz6 7106 cLt

@2437 2034 1s2 AMPPTR INCREMENT POINTER TQ NEXT
G2146 2046 Isz ATIME CINCREMENT TIME POINTER
62144 2a74 . Is2 MASCTR SET OF MASSES DONE?
G2id2 S314 ¢ IMP MSLOOQF NG. DO NEXT ONE
G2i4z 2364-0 Is2 LPQINT ALL POINTS DONE?
$2144 5Szaz oMP CYCLEZ /NQ. DC ANOTHER POINT
62145 1625 TAD ADSTOR

@2146 3766 DCA 1 PLOTF4

G2147 2372 1s2 BUFEND /BUFFER FULL?

$2154 5354 os: IMP RESET “NG. GET MORE DATA
2454 4524 ~ 75 IMS 1 WRTIFIL “WES. WRITE IT OUT.
$2152 9465 5 cee

@2153 S274 Mr BUFSET ¢START NEXT BUFFER.

$2154 41025 RESET, TAD ADSTOR /RESET FOR NEXT SET OF POIN


/SIMPLT.

92e6G
g2604
g2002
92863
a2004
G2665
g2006
62007
g2016
G2644
62012
62613
g2014
$2645
62616
G2oi7
62620
G2G24
G2422
62623
g2024
g2625
42626
62627
920368
42634
O2832
62633
g2034
62635
G2636
G2637
0284@
92844
g2642
92843
62044
62045
B2046
g2647
@2654a
92054
e24a52
62653
92654
G2055
92856
e24a57
92660
92861
g2062
G2463
82864
92065

2088
6462
7624
4432
4544
4424
2348
Geo
4422
6304
6064
4433
6224
6306
7402
7261
3034
1474
3835
1172
3636
3637
4771
4376
3624
4446
3625
1425
1147
7646
S243
2624
7246
1625
3425
S232
4448
1042
3365
4444
3643
3644
7240
3845
3463
7a64
3464
526@
4774
1776
1372
2627
3646
1427
3627

#2008

10F
cAM
vMsS
ams
aus.
MESL

ous
6304
ION
uns
LINE
6306
HLT
cLA

DCA

FNDPLT,

TAD
DCA
TAD
DCA
DCA
JMS
TAD
DCA
TAD
DCA
TAD
TAD
S2A
JMP
Isz
CLA
TAD
DCA
oMP
oMs
TAD
DCA
ums
DCA
DCA
CLA
DCR
DCA
TAC
DCA
oMP
JMS
TAD
TAD
DCA
DCA
TAD
DCA

nm

I

1

TAC

CLA

CMA

PALE-V7 PAGE =

ASTORG
ASTMSF
APL

AINPL

OPENR

GRGNUM
RADD
TRACD
RADD+4
TRADO+4
ABSYRG
RDHORX
44a
TMP
Pas?
TMP2
TMP2
MELEL

té
TMF 4.

TMP
TMP
714
AHDRPL
AMSADD
P2@Ts
ARTORG
PASS
FRSFLG

HYMASS
AYPLT

AXPLT
+2
RDHDRX
Az44
MSDTNX
TMS
MSMTCH
TMP4
TMP4

“SET ORIGIN

FILE ‘

“TURN PLOTTER OFF

COPEN FILE
“NG FILE

@SAVE STARTING BLOCK
(RESOLUTE t GRIGIN

7FIND END OF TITLE

?PLOT TITLE

@SET IN SEARCH MODE - FIRST TIME DLAG
7SET NG MASS FLAG

@READ HEADER BLOCK


/SYMSCN

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PALE-V? PAGE 9

#3408
“SUBROUTINE TO SET NUMBER OF POINTS FOR AVERAGING
NPNTS, @
gms I APL ¢PRINT "NO. POINTS: "
TEXTS
6
JMS I DSEF
NPNTS1. JMS I AINFL READ NUMBER OF POINTS
ums I AbEO
UMS I AGUES ¢FRINT "27"
Mr NENTS /TRY AGAIN
DCA I APNUM
Ms. DIVSET
SKF
UMP I NENTS
JMS I AGUES PRINT "#7"
JMF NPNTS+4
?SUBROUTINE TO SET MAXIMUM RUN TIME
RUNTIM, @
gms 1 APL ?PRINT "RUN TIME: "
TEXT1@
5
RUNTM4, JMS I DSPF
UMS 1 AINPL /READ RUN TIME.
JMS I ADEG
JMS I ARUES
UMP RUNTM2 TRY AGAIN.
SWF
CLA
Muy
P?4
SWF fPUT PRODUCT IN AC
cIA ?NEGATE
DCA TOTIME AND STORE
. UMP oI RUNTIM \
P?4,. 74 PMULTIPLIER TO CONVERT TIME
“TO SECONDS,
PSUBROUTINE TO CALCULATE DIVISGR FOR AMPLITUDE SCA
DIVSET. @
TAD 1 APNUM
CIA
DCA MNUM
TAD I APNUM
ACMC ‘
Muy
F4
szA
UMP I DIVSET OVERFLOW. NUMBER TOC) LARGE
SWP
DCA - DIVNUM
1SZ DIVSET SET PROFER RETURN
UMP I DIVSET
?SUBROUTINE TO SET PLOT SCALING FACTOR
PLTFCT. @
gMS 1 APL 7PRINT "SCALE FACTOR: "


7SIMPLT.

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PALE-V7 PAGE 2-4

THE 4
PoaTe
PoaTZ

INTRVL
F26T2

TMFS
MASNUM
TMP4
HYMASS

NOMSCR
COPMASS.

MASNUM
CRIMAS

SETFLG
TMF4
TMPS
748

MSMTCH
SETFLG
CDPMASS
TMP
MASNLIM
AMSADD
TMP A
M4a
CRTIMAS
TMP AL

TMP 2

+5
TMP 4
TMPS
NOMSCR
AMNMXP
TMP.
CRIMAS
NOMSC1
TMP
CRTIMAS
MSMTCH
HYMASS

PASS

. +3

CRIMAS
PTMASC
CRTMAS

e# GF POINTS IN SET

?GET FLAG

7NG CURRENT MASS

7ADD CURRENT MASS
CMASS=CURRETN MASS?

@SET NO MATCH FLAG

@PREPARE TO TEST IF ALREADY DONE

“ALREADY BEEN CONE
CNG MASS NOT DONE

fLOOK AT NEXT CINE

@STORE MASS AND FIX FLAG


PERCENTAGE OF BASE PEAK

PERCENTAGE OF BASE PEAK

100

50

°
+

100

MASS SPECTRA OF DDT

EI

bey oi ti al nama ian ae a acne eee
100 180 200 250 300 350

C1(CH, )

ohn, so retry
100 180 200 250 300 350
M/e
FIGURE 13, ELECTRON IMPACT AND CHEMICAL IONIZATION


fewer ions with significant intensity under chemical ionization conditions
than under electron impact ionization conditions. Thus, the simpler
spectra give less chance for ambiguous identifications with chemical

ionization mass spectrometry.


“SYMSCN PALS-¥7 PAGE 4

2200 *2260
(CALIBRATION FILE PACKING SUBROUTINE

a2206 @06@ CALBUF, @

o2201 7260 CLA

2202 1356 TAD ADCMAS GET CALIBRATION MASS
62203 3624 DCA AOMASL ADDRESS AND STORE
o2z264 1357 ' TAD ACALST /GET YOLTAGE SETTING
42265 3233 bCA ADSET fADDRESS AND STORE
a2206 1028 TAD ABUFG@ “GET BUFFER ADDRESS
e2207 3853 DCA CBUPFF “RAND STORE

92216 2852 1sz CBUFF @INCREMENT POINTER.
@2211 1453 TAD I CBUFF ?GET FIRST MASS
@2212 7446 SZA “ZERO?

622143 5245 IMP CBUFF1 “NO. CONTINUE

@2214 5604 gMP I CALBUF ERROR RETURN

@2245 3424 CBUFF1, DCA I ADMASL STORE.

2216 2624 IS2 ADMASL INCREMENT MASS POINTER
@2247 7624 cAM “CLEAR AC AND MG.
92220 1254 TAD PS “BUMP POINTER

@2224 1853 TAD CBUFF “BY = AND

@2222 3653 DCA CBUFF “STORE.

92223 41453 TAD I CBUFF “PUT FIRST CAL. WORD
-@2224 7445 ASR “IN AC. SHIFT RIGHT
62225 e404 4 4 BITS.

92226 7524 SHP (SWAP AC AND MG
62227 2053 Isz CBUFF @INCREMENT POINTER.
92230 41453 TAD I CBUFF “ADD 2ND CAL. WORD.
@2234 7524 SWF 7PUT BACK IN ORDER
@2232 7445 DST

G2233 GGG ADSET. 4&@ “STORE

2234 2233 1S2 ADSET

92235 2223 Isz2 ADSET 7BUMP FOINTER BY 2.
$2236 7621 cAM “ CLEAR AC ANG Me
@2237 1254 TAD P4 “BUMP POINTER

62246 1853 TAD CBUFF PRY 4

$2241 3653 DCA CBUFF “AND STORE.

62242 1453 TAD 1 CBUFF ?GET NEXT MASS
2243 7440 ~ SZA ?VALUE=@87

@2244 $245 IMP CBUFF1 NO. PROCESS

92245 3424 DCA I ADMASL “YES. ZERO MASS
@2246 2206 Isz CALBUF “UPDATE RETURN
G2247 Séeae JUMP oI CALBUF RETURN

$2250 GG03 Fz, 3

62251 6664 F4, 4

/SUBROUTINE TO DETERMINE ROD VOLTAGE SETTINGS
@2252 o606 CALIE, @

62253 3416 DCA SMASS STORE MASS

62254 1116 TAD SMASS

62255 7424 ACNC “PUT MASS IN M@

$2256 3354 DCR NPOINT ¢ZERG POINTER

G2257 1356 TAD ADCMAS GET CALIBRATED MASS STORAGE
42260 3366 "DCA ADMAS2 ADDRESS AND STORE.

62264 1768 TAD I... ADMAS2 “GET FIRST CALIBRATION MASS
82262 7457 SETCA1, SAM , (SUBTRACT FROM STORED MASS

$2263 7450 SNA CAC=a? CMASS=CALIBRATION MA


SECTION III

INTRODUCTION

The goal of this project was the development of a practical system for
application of "Selected Ion Monitoring" to gas chromatographic analysis
of pesticides.

Selected Ion Monitoring (SIM) is the technique of monitoring one or only
a few ions from a mass spectrum rather than acquiring complete mass
spectra. The technique has been demonstrated magnetic deflection mass
spectrometers, (174) However, magnetic deflection instruments have one
serious drawback for development of this technique to its ultimate; it
is difficult to change from one mass to another quickly by changing the
magnetic field strength because of the hysteresis of magnet systems.

The LKB mass spectrometer, for example, employs a change of the acceler-
ating voltage to focus on different masses. This limits the masses that
can be monitored to a range of about 10 percent of the mass. If a
larger mass range is covered, there are significant differences in the
sensitivity to the various masses.

The quadrupole mass spectrometer is well suited to the peak-monitoring
technique because all that is needed to change from one mass to another
is to change the voltage on the quadrupole rods, The Finnigan mass
spectrometer in combination with a computer data system such as the
System 150 provides an ideal system for development of a Selected Ion
Monitoring mass spectrometric technique.

Chemical ionization mass spectrometry is also ideally suited to the SIM
technique. It appears that chemical ionization gives higher sensitivity
than electron impact ionization, In addition, most compounds produce


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PALE-V?

2

PAGE 2-

“NUMBER OF FOINTS FER MASS
/NUMBER OF SETS OF MASSES.
(NUMBER GF MASSES

“MASSES TO BE MONITORED.
@INTEGRATION TIMES
712@5 WORD BUFFER
“SETTINGS FOR MONITORED MASSES
SMOOTHING BUFFER

STARTING CA

6eea.

@PACKED CALIBRATION FILE POINTS -M

“ROD SETTINGS


Get No, of points -
double tt

Divide max
buffer length

by
2X No. of point

Negate&
store

Get quotient ~
multiply by
2X No, of points

[ store ]
Fil buffer

with zeroes
(subroutine ZROFIL)
T

‘Tum MS interface on

Set Pri, buffer pointer

Get No. of sets of
points

Get No. of points per mass

FIGURE 6. FLOW CHART FOR MASS-SPECTROMETER-SCAN ROUTINE

16


Enable teletype|
output

r
Print: “calibration
file:"

Read calibration
file name
I
Store calibration
file name
J
Search system
directory

No

File found?
Print "22"

Yes
Read file into
core
I
Pack calibration
file buffer
(Subroutine CALBUF)

Read masses and
integration times
(Subroutine STINIT)

[-

Galculate rod voltages
(Subroutine SETCAL)

Print:

Read & store title

i
Print: "data file
name’

+
Read and store data file
name

earch system directory|

"Title" (of run)

Yes

File found?
© fou Print: "duplicate

file name"

Write file
pheader block

i
Initialize Plotter and
lower pen
(subroutine PLOTIN)

Es)

FIGURE 2. FLOW CHART FOR PROGRAM INITIALIZATION
iL



ACKNOWLEDGEMENTS

Assistance of personnel of the Southeast Environmental Research
Laboratory is gratefully acknowledged. Their experimental evaluation

was of great help in debugging the computer program.

Dr. Rodger Foltz of the Columbus Laboratory of Battelle Memorial

Institute aided in the development of design parameters for the

computer programs.


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“SET TOTAL TO @
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SIGN @SET FOR + COEF.
ROTAT
COEFSM /CHECK FOR - COEF.


&SSMSCN ‘ PALS-VF PAGE 14

4400 +4408
SUBROUTINE TO HANDLE DATA CURING M.S

INTERFACE INTEGRATION.
B440G 8688 CHKSET, &

B44H1 4455 TAD WTFLAG .°GET WAIT FLAG

B4402 7516 SPA “USE THIS POINT?
O4403 527s JMF WAIT2 eNa,

84404 42235 TAD PLOTFT

4405 7658 SNA CLA “POINT TO FLOT?
G4466 5265 oMF WAITL “Na,

@447  add4 TAD SETFLG

G441@ 7650 SNA CLA TIME TO MOVE POINTS?
G4444 S234 oMP PLOTPT~12/°NOQ. CALCULATE POINT.
G4442 4414 DCA SETFLG CLEAR FLAG. .
M4443 1374 : TAD NSMOOT GET NG POINTS TQ SMOOTH9
G4444 7ad4 CIA ,

44445 Paar TAC

Q4416 3372 DCA CTR 7SET COUNTER (-NSMOCT+1>
Q@4417 1456 TAD SFTBLF

G@4420 2286 bCR PTBUFG@

@4421 14154 TAD SPTBUF

Gd422 7oGd TAC

B4423 3307 DCA PTBUFL

4424 4707 RLOOF. TAD I FTBUFL ¢GET VALUE.

G4425 3706 DCA I PTBUFG MOVE IT DOWN.

G4426 2272 Isz CTR ?DONE?

G44a7 74d SKF ena.

4426 S2i4 JMF PLOTPT-42

G4431 2306 1sz PTBUFG@

G4432 2207 1s2Z PTBUF A

B4433 Saad oMP RLOOF

B4434 7665 DLO

B4435 @G8G PLOTFT. @

B4436 4475 vs T MULTI

G4437 aae2 FACTOR

B4440 7402 HLT MULTIPLY OVERFLOW.
G@4d441 0 4455 gMs 1 DIVIDI

G4442 BOSE DIVNUM

S444 7724 MGAC

O4444 3452 DCA I BUFLOC STORE IT.

4445 2235 DCA PLOTFT /¢ZERC FLOT FOINT ADD.
64446 2185 Isz PICTR ENOUGH POINTS TO SMOOTH?
Gd447 7414 SKF “Ng.

4456 5252 JMF SMOOTH “YES.

B4454 2052 1sz BUFLOC ¢BUMF STORAGE FOINTER
@4452 5265 IMP WAITS

64453 4316 SMOOTH. JMS FIT PCALL SMOCTH ROUTINE.
@4454 7366 PLTBUPF “ARRAY ADD

@4455 3266 | DCA PLOTPY'

O4456 4507 ~% gms 1 PLOTT @PLOT POINT.

44457 9904 PLOTPx, @

G446G 4806 PLOTPY, @

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B4462 7348 NL? PPA fACE-L

B4462. 3165 DCA PICTR PRESET COUNTER.


Flow charts for these routines are shown in Figure 9 and 10,

Keyboard Monitor. A keyboard monitor allows the operator to change
parameters during data acquisition. The allowed commands are:
1. E(CR): End run, insert E-O-F and catalog file
2. Sn(CR): Change to set of masses n where n = 1,2, or 3
3. WNn(CR): Change number-of points to n
4. Fn(CR): Change scale factor to n
5. Tny,n9,---ni(CR): Change integration times to Ny »Mg--ny
6. Control-L: Abort, do not catalog file

A flow chart for the keyboard monitor is shown in Figure 11.

Plotting Program

Since the on-line data acquisition program can plot only one mass from
each set, an off-line program plots all data points. This program scans
the entire data file prepared by the data acquisition program and deter-
mines the proper scale factor to keep the entire plot on scale. The
minimum value is considered to be baseline and subtracted from all values
for baseline suppression. It then makes a second pass through the data
and plots each mass sequentially in the order data were acquired. ‘Two
output options are provided to the operator. After each mass is plotted,
the prompt "CHANGEPEN." is printed by the teletype. If the operator
wishes to overlay the plots using different ink colors, he should change
the plotter pen and press the RETURN key. If he does not wish to overlay
the plots, depressing any key other than RETURN advances the plotter
chart about three inches and plot the next point. A flow chart of the

program is shown in Figure 12,

21


SECTION V

COMPUTER PROGRAM DEVELOPMENT

This project was devoted to development and evaluation of computer
programs for implementing compound specific mass spectrometric detection
on a Finnigan mass spectrometer equipped with a System Industries

System 150 mass spectrometer control system. This report describes the
overall programs, flow charts for the overall program, and more detailed
flow charts for the individual segments. Program assembly listings are
given in the Appendices,

The programs will operate with either disk or tape-based systems. Of
course, the disk system provides room for more data storage. However,
two DECtapes provide ample storage for any normal run. Two programs
have been written, one for data acquisition (including on-line present-
ation of the first mass specified, using the Houston digital plotter) and
one to plot all data points to the same scale . These programs are dis-
cussed below. The programs are designed to operate on a 4K PDP8/e computer
equipped with the KE8E extended arithmetic element (EAE). However, since
the EAE is not required for the System 150, versions that do not require
the EAE have been written for both programs. The non-EAE data acquisi-
tion program is not noticeably slower than the EAE version for most
applications. However, the non-EAE off-line plotting program is notice-

ably slower.

Data Acquisition Program

The program provides for monitoring from one to eight different masses.
The integration time for each mass can be specified separately to avoid
saturation for strong peaks while providing required sensitivity for weak

peaks. For improved signal-to-noise ratio on weak peaks without danger


SECTION VI

SYSTEM PERFORMANCE

This section describes system operation and presents results obtained jin
this laboratory.

The SIM programs are called as USER programs on the System 150. A typical
dialogue for a SIM data acquisition follows with operator responses under-
lined: (Each response is followed by a carriage return).

SYSTEM 150 IS ON SELECT MODE: USER

LOAD FILE: SIMSCN

CALIBRATION FILE: CAL-H

MASS(ES): 243,209,279.292

INTEGRA, TIME: 100

ANOTHER SET?N

NO. POINTS: 3

RUN TIME: 3

TITLE: GC-MS (CI-CH4) OF PESTICIDE MIXTURE
SCALE FACTOR: 50

DATA FILE NAME: Nel
DATA

A sample of the plotting program dialogue is given below:

SYSTEM 150 IS ON SELECT MODE: USER
LOAD FILE: SIMPLT

FILE? Nel

CHANGE PEN (CR)

CHANGE PEN (CR)

CHANGE PEN (CR)

CHANGE PEN (CR)

26


“SIMPLT. PALE-VF PAGE 7-2

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z264 PAGE


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SMF

TMF

CLA CLL
TAR

SHA CLA
IMP I
TAD

TAD

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TAD

BCA

IMF I
FNDFLT
TAD

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vMF

TAD

SNA CLA

me

Pésae
SPCAGL
NFTS
NFTSZ
SPCADD

EQREOF
PASS
+4
ARGCL

SPCADD
INTRYL
SPCAGD
NFTSE

SRVEYS
ROINTS
SRVEVL

Pre?

ENDPFIL
M5
NPTS2
SPCADD
Méesaa
NPTSE

Mee
_-4
NFTSS
ABK2TH
RADE

NFTS2
RACE +d

RAGE
RAD
ABK2TH

HYMASS

STLDOT
PASS

e# OF SETS“ELOCK

“FOUND EQR OR EOF

“SET PEN UF

eSET Ys@ 1 MOVEMENT § FEN

“NEEL MEW BLOCK

“EOR

“SET RETREAT TO 3 BLOCKS

“COMPUTE # TO RETREAT

7NO MASS

- CHECK PASS

ipod

a


of saturating strong peaks, a selectable number of consecutive points
for each mass can be added together and stored as a double precision
value. The value for the first specified mass is plotted to give a

real-time chromatogram.

This program is designed to be called as a USER program on System 150,

and uses standard System 150 mass-storage read, write, and file handling
routines, standard teletype and plotter routines. These subroutines are
the property of System Industries and therefore not discussed or listed
in this report. The multiply ‘and divide routines that are based on the
EAE option are included in the program listing, but are not flow charted

or discussed.

The program consists of five basic segments:
1. Initialization,

2. Mass Spectrometer Scan Control,
3. Data Recording,

4. On-Line Data Presentation, and
5. Keyboard Monitor.

A number of smaller subroutines are used to implement input, output and
other functions, The overall flow of the program is shown in Figure 1.
The individual program segments are described in the following sections.

Initialization. The initialization phase of the program sets all initial
parameters for data acquisition. These are:
1. Calibration File Name. This program assumes the
presence of a standard system calibration file.
2. Masses to be Monitored. From 1 to 8 can be specified,
decimal fractions permitted.


ststsis)
1285
628g
PESTS 15)
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76

INTRO,

FLUSH,

M4QP34,
PRESEC,

PALS-VF

MAITS

ATRNON
ROHEDR

READS

WAITS

ATRNON
INTRE

ATRNON
ADPLOT

ADFLOIT

AGELOT

ADPLOT

ADFLOT
SETORG

ANSADD
TMP!
M4aQPs@
THRE
THR
TMEL
THP2

FLUSH

PESGG.
SETORG
SETORG

EREFN4

PAGE 7-1


“SIMPLT.

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PALS-Y? PAGE 9

Mie
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ALINE
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TMF

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THF S
TMFS
PRMAICH
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MREGUT

INFL+4
PLge

CRTCHK
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+6

2
TMF2
BLBL
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CRTICHK

TMF.
TMP
TMP2
TMP
MASKE
P4a
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TMPS
MCRTRN

w+6
TMPS
PRN1CH
LINEFD
FRNICH
INFL

“FILL BUFFER WITH BLANKS

WAIT FOR CHARACTER
“GET CHARACTER

“ECHO
“RUBGUT ?

“POSITION OF LST CHARACTER

fFLAG WAS -1 - RESET To -z

FLAG WAS

@ o- MAKE -4

CCARRIAGE RETURN?


SELECTED WATER Ber tis

RESOURCES ABSTRACTS Ww

INPUT TRANSACTION FORM
Specific Ion Mass Spectrometric Detection for Gas s F «1D. November
Chromatographic Pesticide Analysis A 1973

8. Perform: Orean rion

Repuri Se

Maynard B. Neher and James R. Hoyland
yn 4 G-8309-1

Battelle-Columbus Laboratories
R-800909
13. Tyree’ Peco ind Final

Periou Covered

” U.S. Environmental Research Laboratory July 1, 197% ehyy,June

12. Sponsorins Orcanie:

Environmental Protection Agency, report number,
EPA-660/2-74-004, January 1974.

Computer programs have been developed for a PDP8/e controlling a Finnigan 1015
quadrupole mass spectrometer to monitor selected ions from components in a

gas chromatographic effluent. The program is designed to monitor only a few
ions (1 to 8) to enhance the sensitivity for the selected ions. Signal-to-noise
levels of 10:1-30:1 have been obtained for 0.2 ng or less of four pesticides
employing chemical ionization mass spectrometry and a digital smoothing routine.

This report was submitted in fulfillment of Project Number 16ADN 28, Grant
Number R-800909, by Battelle Memorial Institute under the sponsorship of the
Environmental Protection Agency. Work was completed as of June 30, 1973

Ia. Daseri; cors

Mass Spectrometry* Computers*
Gas Chromatography* Data Processing*
Pollutant Identification* Organic Pesticides*

Organic Compounds*

Lientifter.

Specific Ion Monitoring*

Gc/Ms* -
Computer Control*

Pesticide Mixture

Pk Beeld & Grou: 054

19. S ourtty Class. a1 Baot Send To:
(neparts Pages

. 43 WATER RESOURCES SCIENTIFIC IN:
20. secur y Class. as Bice U.S, DEPARTMENT OF THE INTERIOR ATION CENTER
C" zey WASHINGTON, D. C. 20240
| M, Be Neher I Battelle Memorial Institute



SSYMSCN PALE-¥ PAGE 1@

#3608
“SUBROUTINE TO CALCULATE CONSTANTS FOR CATA ACGUISI
CCONST, @&

TAD 1 TMASS “GET NC. OF MASSES

CLL RAL “MULTIPLY By 2.

OCA PNTLEN : .o
TAD Fiza eMAS. BUFFER LENGTH
ACMC /PUT IN MG@

OWI

FNTLEN

S2L

HLT “DIVIDE ERROR.

SWF *GUCTIENT TO AC.

CIA “NEGATE

OCA MLEN *NUMBER CF SETS OF POINTS.

uMP I DCONST “RETURN.
Piz65, 1285
fYERE ROUTINE TO DIVIDE UNSIGNED DOUBLE PRECISIION
PDIVIDEND BY UNSIGNED SINGLE FRECISIOM DI¥VISOR
“CALLING SEQUENCE:

? AC CONTAINS HIGH ORDER DIVIDEND.

e M@ CONTAINS LOW ORDER DIVIDEND

é gas 1 (DIVIDE?

? DIVISOR ADDRESS
Gzé1? GHG DIVIDE: @
B3626 43246 aM SIGNL
S624 P52. SWF /PUT MSH DIVIGEND IN M@.
@3é6é22 3266 OCA DIVIL eSTORE LSH DIVIGEND
Gz623 1647 TAD I DIVIDE /GET ADORESS OF
@3624 3264 DCA OIvil2 fDI¥ISOR AND STORE
G2625 1664 TAD I DIVTS “GET GI¥ISOR
G2626 4336 IMs SIGNe
S262" 2264 OCR DIVIz 7AND STORE
G2630 74a? OVI
G3624 3661 biVig
-@3622 74a S2b

7462 HLT “DIVIDE ERRCF

Q@z6z4 7524 SWF “MSH TO AC. REM TO Me.
G2635 3262 DCA DIYIs “STORE MSH GUCTIENT
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G3e6e3? 7524 SuF ?FPUT IN PROPER ORDER
2646 7467 DMI
Gzedi 3664 OI¥T2
Gz642 P48 SéL
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G3644 71d CLL RAL 7MULTIPLY REMAINDER BY 2
@zé45 7H44 CIA ? AND NEGATE.
@z646 1264 TAD bIvIg fADD DIVISCE,
Q3647 7756 SPA SNA CLA “DIVISOR. GE. REMAINDER?
$2654 5252 JMPF + Na.
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“SYMSCN : PALE-Ve PAGE 14-2

@454? 3354 TOTAL :

84556 4455 ums 1 DIVICI CALL DIVIDE ROUTINE.
64551 G6GG SML2, ts]

84552 7568 SMA “AC. GE. @?

84553 5356 uMF +5 , VES. 5

84554 7624 can “NG. SET=@!

@4555 57414 IMF ‘T FIT “EXIT

G4556 7446 SZA CACHE?

@4557 7462 HLT CNC. OVERFLOW ERRCR.
4456 41376 TAD PAP aa

84561 7457 SAM

94562 ria SFA CLA “TQQ LARGE?

B4563 5366 oMP .+S ena.

G4564 4376 TAD Pirea “VES,

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B4566 red MG@AC “YES, GET GUCOTIENT

a4567 5716 JMF I FIT’: ANG RETLIPN.
B4576 1760 FAraa, i17aa _

S4574 G@G45 NSMOCT, 43

a4572 @66G CTR, a

S4572 GaGG SMADD, &

G4574 866 FACT. a

B4575 3256 AFACT., SYTGLY


Get address of
mass storage file

Get address of
time storage file

Get address of file
for storage of number
of masses

Clear No. of masses pointer

Clear No. of sets counter = 1

Get masses
(Subroutine MASSET)

I

Calculate and

Get times
(Subroutine TIMSET)

x _<?>
‘Yes

pointers by $1
(octal)

T
L______
Set pointer to
firs set of masses
and times

(Get No, of points to add
(Subroutine NPNTS)

Get total run time
(Subroutine RUNTIM)

FIGURE 4. FLOW CHART OF SUBROUTINE FOR INPUTTING MASSES,
INTEGRATION TIMES, TOTAL RUN TIME AND NUMBER OF
POINTS TO SUM

13


“SIMPLT.

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#3208
SPOCTD,

LOOPSD,
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NONZERO,

STORIT,

SECNDC,

INCRSP,

OCTNUM,
ADDSSF,
MTHOU,

@
ocAR
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-1750
-144
-12

PALE-V7 PAGE &

QcTNUM
SPOCTD
ADDSSF
SFOCTD
ICHFOT
GOTONE
AMTHOU
CURNT
M4
KPTRAC
DECCAR
OcTNUM
CURNT

+5
DECCAR
GOTONE
ocTNUM
INLPSD

DECCAR

NONZRO
GOTONE

NONZERO
Psocaa
DECCAR
STORIT
Pea

DECCAR
ICHPOT
CLL

SECNDC
ICHFOT
DECCAR

ADDSSF
INCRSP
ADESSF
DECCAR
ADDSSP
ICHFOT
ADDSSP
CURNT

KPTRAC
LOOPSD
SPOCTD

“STORE NUMBER

“ADDRESS FOR RESULT

/?@ CHAR. FOS. ANG PREY. CHR. FLG
¢ADD, OF -1800

?-4

7DONE WITH CURRENT POWER QF TEN
7a?

fPREV. NON-ZERO?
“BLANK

fBYTE SWAP


On-line data No
plotting routine

MS ready for
output

Reset voltage
array address

Smoothing
buffer ful?

Get value ~
move it down

Bump pointers
and counters

Plot point

Reset buffer
counter - and
buffer-full flag

ae |

FIGURE 7. FLOW CHART FOR ON-LINE DATA PLOTTING ROUTINE

18


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ra

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aes ITIME

“RETURN IS TO JMS+4
?TIME CAN BE BETWEEN @@@e AND rrr?

MSSET;

“SEND MASS NO. TO
NUMBER IS STORED IN LOCATION SPECIFIEC BY
fAMPLTD WILL CONTAIN NEW AMPLITUDE AFTER
fIF CASETT? EXCEDES @aar

a
CLA
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Kir
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PAGE S-1

IN KEYBOARD?

Na.

“VES. PROCESS IT.

“SET LOWER & BITS OF TIME.
“SKIF IF MS Is NOT READY
“POR INPUT

“CLEAR TBR AND SEND LOWER &
“ROTATE UPPER BITS OF
?TIME INTO LOWER AC

“MASK OFF UPPER PART OF AC
“ADD CONTROL CODE
“SENG TO UFFER IER

INTERFACE AND GET AMPLITUDE BACK

ASETT.
RETURN

F7r? OR IS NEGATIVE AN ERRO

eWILL RESULT IN THE ¥YALUE SENT TO THE IER

KP.
Ki?
Ke4a,
Ka4a,

RDTTY, .

CLA CLL
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Isé

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346
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ASETT
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RTL

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“CLEAR IBR. SEND LOWER & BI

“MASK

?GET UPPER HALF.

“MASK
“ROTATE INTO POSITION
“ADD TO OTHER FART

“SEND TO UPPER IBR

“JUMP TO BACKGROUND ROUTINE

SUBROUTINE Ta READ MASSES

MASSET,

a
DCA
TAD

NMASS
TADMAS

“ZERG COUNTER.
“GET AND STORE START


“SIMPLT. : PARLEY PAGE 6-41

B26é66 Gouna NFTSS, &@
G@2é6r 2436 EREFX2, EOREOF
Bsera Gana INTCRT. @
B2671 aoa48 a
B2e72 30868 ARGCE, RGCPLT
2673 2554 AEBLKe:. ECBLOK
B26e74 2166 BPeatTe, PeatT2
G2e75 G60G Pe2eéT1, &
B2676 G606 PLTIMAS, &

B2er?7 reee CLA

G27ee 41654 TAL CRIMAS
B27at 4744 vMs I ASFTCD
B27a2 Gadd COMASS

G@aras Ada TAD M46
G@2ra4 2254 OCA XMSCLE
G@27a5 1z32 » 4 TAD YMSCLE
B27eée 1346 TAL MHUN
@27ar 3352 DCA YHMSCLE
G@271a d1d4 TAG COMASS
B27i1 a1e7 AND NP?
@27iz 4225 uMsS PLTNUM
27143 1445 TAD COMASS+4
G@27i4 Paae rea “EYTE SWAP
@2745 o427 AND N7F
G@2716 4322 agMs PLTNUM
G2ri7y 44145 TAD COMASS+4
G@2726 G427 AND NP?
G272l 4222 JMs PLTNUM
G27a2 Sere JMP I PLTMAS
G2722 80G FLTNUM. @

G@2r24 3334 DCA LTSTOR
B2725 iszd TAL MMSCLR
B2726 A1zz7 TAD Po

B@2r27 3234 DCA xMSCLE
B273a 4745 ums 1 ADDLTR

G27s1 GaGG XMSCLR, @
B27z2 8OGG YMSCLR, @

G273e aaae z

@27s4 Goa LTISTOR. @

B2735 gana g .
B2736 S72z JMP J PLTNUM
Ga7s7 G12 PS. iz

S274 7700 MHLIN, ~166

@27di r7r2z Md4é, 56

@2742 3146 APRSC2, PRESRC
B2743 4660 ADDLTR, GLI
2744 3246 ASPTCD, SPOCTD
oe
Ba777 612
3466 PAGE


Using methane CI gc/ms the best results so far have been obtained with
Parathion and DDT. The limit of detectability for DDT is about .01 ng
(10 pice grams) and about 0.002 ng (2 picograms) for Parathion. Precise
limits of detectability have not been determined for either. For elec-

tron impact gc/ms the detectability limits are higher.

Figure 15 shows a CI gc/ms SIM plot for a mixture of 1 ng each of DDT,
DDD, Parathion, and Dieldrin. The real time plot of m/e 243 shows two
peaks. The first peak is for Dieldrin and is about 30 percent of the
second peak (DDT). The reconstructed plot shows the relative retention
of the four pesticides. The plot also indicates that DDD gives the
highest response and Dieldrin, the lowest. ,

The SIM technique has also been applied to drug analyses using methane
CI. Clarke and Foltz (6) have used the technique for analysis of morphine
using a reverse isotope technique in which dg morphine is used as a
carrier. In a comparison study of SIM with some of the commonly used
morphine quantitation‘ procedures, TLC, GLC, spectrofluorimetry, radio-
immunoassay, hemaglutination, inhibition, and Auto Analyzer), SIM was
found to be at least as sensitive as the radioimmunoassay (RIA) technique
but more specific, The RIA technique will detect other opiates as well
as morphine, whereas the SIM technique is specific for morphine. Detect-
ability limits have been set at 25 ng/mt (7) for RIA. The SIM technique
detected 5 ng/ml without special attention to the instrumentation. The
lower limit of detection was not determined, but is well below 1 ng/ml.

30


These steps, while part

of the logic for SETCAL,

ate actually in a separate
subroutine because of

core -page size Limitations

Set pointer fo L
last calibration

‘mass Get mass to
be calibrated ~
L store

Get previous I

Jcalibration mass|

Get first
. L.. .

mass again ~
‘Subtract From put in MQ -
mass to be clear AG
calibrated T
. ‘Set calibration
Store mas difference No, counter = 0
“Get previous Get addvess of
calibration mass first caltbratton
mass point

and store pointer
[eee] [

Gee first
‘Add next calibration mass

calibration mass

I se

Subtract from

‘Store calibration mass to be
mass difference calibrated

[ (in iQ)

Get calibration

=0
Yes
Get calibration
‘Rad start address polnt counter po
of rod voltage No
calibration file
[[Dounte « | Increment
Store next calibration calbation
ae ‘Add voltage and calibration
] calibration file mass pointer
‘Subtract two to starting address TL
form previous T <a
calibration voltage Cent
address = store it ‘Store ealibration ene
L value pointer
DoF ad prevent al Ne
calibration voltage D. P. load
voltage senting
— Yes
1 al
Teena Ti or
SETCAL message
D. P. add next
calibration voltage

Multiply by
mass difference

Divide by
calibration mass
difference

D. P. add previous
calibration voltage

Ld

FIGURE 5. FLOW CHART FOR ROD-VOLTAGE-SETTING SUBROUTINE

14


“SYMSCN ‘ PALE-VF PAGE 8-2

G@szer P31 NL@Gat “SET AC=1
Q333G «4567 ams I PLOTT “DRIVE PLOTTER FEN DOWN TC
G3331 Bane & 7X ARIS
G@3332 6636 -1750 -
@3333 7348 NL? FPF CACE<4
G2334 4567 JMS 1 PLOTT . “SET NEW CGRIGIN
G3335 7sa4 NL@@G4 ?SET ACH
@3336 4567 ums I PLOTT “RAISE PEN 1" ABOVE
@3337 eaae & OR ARIS.
Q3340 41648 146
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O3342 4567 gms I PLOTT 7SET NEW ORIGIN.
G334s 4548 vMs I APENON LOWER FEN
G3344 17523 TAD I NSMOTI ¢FOINTS TQ SMOOTH
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@3346 3185 DCA PTICTR “SET POINT COUNTER.
3347 1116 TAD oO? OP TEUF CSET PLOT BUFFER
$3356 3652 OCA BUFLOCG ¢ POINTER.
@3354 6664 TON
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63355 4664 a
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@3374 655 655


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FAGE 17°


“SIMPLT. . PALSY? PAGE 19-4

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\


SECTION I

CONCLUS IONS

Two computer programs have been developed for selected ion monitoring

of gas chromatographic effluent components with a Finnigan 1015 quadru-
pole mass spectrometer equipped with a System 150 data system, The programs
are designed for a PDP8/e (or PDP-8/f£ or PDP8/m) computer equipped with

the extended arithmetic element (EAE). With these programs, signal-to-
noise ratios of 10:1 to 30:1 have been obtained for 0.2 ng or less of

four pesticides employing chemical ionization mass spectrometry and a
digital smoothing routine. Programs are also available with EAE

simulgtor routines for computers without EAE. These programs have

been debugged and are ready for general distribution.


/SIMPLT

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PAGE 5-2
¢CHECK QF END OF BLOCK

“FOUND EOR OR EOF


?SYMSCN

6362
6364
6364
63714
6372

7304
7305
7328
730?
7340
7344
7346

7524
7724
?764
7424
7622

PALE-V7 PAGE 2

gSYMSCN

/THIS PROGRAM IS WRITTEN FOR A POP &/E

/COMPUTER, FINNIGAN 4645 MASS SPECTROMETER

7AND Al SYSTEM 15@ INTERFACE. THE

7PROGRAM CONTROLS THE MASS SPECTROMETER

7TO PROVIDE MONITORING OF FROM 1 Ta

“PEAKS FOR SELECTABLE INTEGRATION TIMES,

@WITH FRACTIONAL MASSES PERMITTED. FOR SYSTEMS
“WITH THE KES=E EXTENDED ARITHMETIC ELEMENT, ERE,
@GEFININE EARE=4 DIRECTS ASSEMBLY OF A PROGRAM USING
?THE EAE INSTRUCTIONS. IF EAE IS NOT DEFINED ¢ OR
(DEFINED ERE=@ > SIMULATOR ROUTINES WILL BE ASSEMBLED
?THAT GO NOT NEED THE EAE.

,

“WRITTEN BY:

MAYNARD B. NEHER

BATTELLE COLUMBUS.

S@5 KING AYENUE

COLUMBUS, OHIO 432014

644-299-3151 EXT 1693

NWVANAN

/7PLIST CONTROLS LISTING OF THE S.1. PLOTTER
?ROUTINES. IF NOT DEFINED ¢ OR DEFINED E@UAL

?TO ZERO > THESE ROUTINES ARE NOT LISTED. IF DEFINED
/NONZERO, THE PLOTTER ROUTINES ARE LISTED

?

IFNDEF PLIST <PLIST=@>

é
,CDEFINITIONS FOR 15@ INTERFACE I0TS

?
MSIC=6362 ?CLERR IBR

MS1=6364 ?INFUT TQ IBR

SKM1=6361 @SKIF IF NOT READY FOR INPUT
SKMO=6374 ?SKIP IF NOT READY FOR OUTPUT
MSO=6372 OUTPUT OBR

?

/MISCELLANEOQUS DEFINITIONS

2

NLO@01=7304 + ARCEL

NL@982=7305 PACS

NLOGO3=7325 PACER

NLO@04=7307 efit=4

NL??7727340 ?ACE=2

NL?776=7344 PACE-2

NL?7?75=7346

é -

/ERE DEFINITIONS:

?

SHP=7524

MGAC=7724

MGAR=?704

ACMC=7424

CAM=7624


“SIMPLT.

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SSYMSCN PALE-VF PAGE
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ga054 Mé6G6 CLOSEX, CLOSE
@aa55 3647 DIVIDI. DIVIDE
ABGSé6 BAGG CIVNUM, &
aaas? 2472 DSPF, SPF
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aa@61 4200 EXECX, EXEC
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aa10@ agee@ NTIME, @
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g0127 146 TTRD,  TTYIN
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62133 0404 WRITEX, WRITE
60134 3542 WRTFIL. WRTDAT
60135 8800 WIFLAG, @
@0136 3867 ZROFLI, ZROFIL
7FLOTTER COMMANDS.
@6137 4244 APENUP, FENUP
@644G 4220 APENDN, PENDN