Document Rd0ZK8Gn5nK565oD25bKeJXn
T tT U ti ANALYSES OF nrriC M SCALE D IC m .O PO AN IM *"E
Monsanto
MONSANTO COMPANY / DAYTON LABORATORY / DAYTON, OHIO 45407
ESC/PAYTON____ (Depar tient/Section)
. -^AtYUCAi (Typ of Report)
REPORT HO. : HDA - 515 JOB/PROJECT HO.: 484.5010
DATE- 6 August 1934 PERIOD COVERED:
RECEIVED
AUG 1C 1964
HOMIAMTO CO****Y OVrtfcN, **'! Ih T LOUtf
TITLE: AWALYSCS CF BELCH SCALE DICHLOfWMLJNE BtP!'
AUTHORS: S. L. Marcr
ABSTRACT: Samples of dichloraniline wastes ar.d their
bench-scale pyrolysis products were sub.-ittod by f'.IC for GC/IIS analysis for specified crgar.ic corpounds. Tf.e results of these analyses are shown in this report.
*A I < Vi
*s
i
TECHNICAL APPROVAL!
(*{' ____ Oi V, Brooks Senior Research Group Leader
APPROVED BY t
___ _
R. F. Ivory^
_____
Environmental Sciences Center Service Project Manager
APPROVAL DATE *
$'/* / t____
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HOMS 220806
DISTRIBUTION
COPY NUMBER
1 D. Kelsall 2 R. F. Ivory
3 5. L. Mazer
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M2B
1250 1250 1250
R2C
____ abstract only
H. A. Woltermann
NOTE;
Distribution of this report is restricted. Requests for additional copiss should be madT through the principal
contsct at the Monsanto Iocstion involved or the Manager, Environmental Sciences Center, Dayton Laboratory, Dayton, Ohio.
ACKNOWLEDGEMENT
Contributions of the following Dayton Laboratory personnel to this project are gratefully acknowledged;
Analysesi
S. Barksdale S. L. Hater D. McKenzie ft. Hoble ft. Williams
COMPANY COlNiriDLNTlAl
MOMS 220807
*501 17 sS*
ANALYSES row:
TETOACHtOROPHtNAZlNES TETfiACMLOROeEHZlOIRES/TE TRachlOROSE HI DINES POLYCHLORINATED biphenyls
MOMS 2208OB
BSOl OiSN
i. introduction
Sample* of dlchloroanlIIne Mattel and their bench - tcale .lyrolytl* product* Mere *ubmltted by NIC for GC/S analyte* for tetrachioroohenazlne*. tetrachlorobenzldlne/tetrachloroemldlne*. poIychiorinated biphenyl * (PCB). tetrachlorodlbenzo-p-dloxln* (TCDD*), and tetrachlorodlbenzofuran* (TC0f), Tne pyroiviI tample* reiulted from heating of dlchloroanlIIne Matte* at varlou* temperature*, and varied In type from a product that reet>led the original watte to one that wa* primarily a char or carbonaceou* Material. Because of t h I * variation In the organic carbon content among the tample*, a* Mel I a* the variation in the level* of the analyte* m tne sample*. a hot of workup method* Mere required to prepare the jample* for GC/HS analyte*. tm tectlon of thi* report ! 11 deal Mlth method* of analy*!* for tetrachlorophenazIne*. tetrachlorobenzldlne*/tetrachloro*em<dlne*. ary) PCB, While *ome common extraction* done for PCB*. TCDOi, and TC)f are decrlbed In thl* tectlon. the further cleanup and analytl* of thete extract* for TCOD* and TC>f* are deteribed In a later *ect!on.
HONS 220809
OSOIIJtSM
II. SANPU PREPARATION NCTHQOS
rne analysis goal for this project was Quantification of total isomers of each analyte type down to the I m level, This requirement necessitated ff*jch lower detection limits on a per Isomer basis, since each compourp class included from 22 to 6S0 isomers. Table | details the rubber of Isomers for each compound class, and the per Isomer detection limit required to achieve the l ppm total Isomer content goal. It should be noted that analysis for tetracnlorosemidfnes was not specifically requested for this project, but since these compounds are not distinguishable by mass spectrometry under electron Impact Ionization from the Isomeric tetrachloro* benzidines, they had to be Included In the analysis, and this further complicated detection limit problems.
Sample preparation methods for low levels of PCBs, TCDOs. and TCOfs are used routinely In the EnvIronmental Sciences Center at the Oayton Laboratory, but low*level methods for tetrachlorophenezlnes and tetra* thlorooeniIdlnes/tetrachlorosemldlnes In organic matrices had not yet been devc'ooed. * method was develooed for the ohenazlne analysis for this protect. Tr.ij method Involved modi fleet Ion of workup procedures normally applied for analysis of the stuctufally similar dioxin. Method development for low*level analysis cf the semidlnes/benzldines was predicted to be a sizeable undertaking and the decision was made bv MIC to forage funding of such a project at this time.
The attested workup methods for tnese samples followed an orderly sequence from easiest and least time-consul ng to hardest. In general, a simple sample dilution or an extraction without solvent concentration was attempted first, if the analytes were not detected (n this "extract", lower detection limits were obtained by using Soxhlet extraction (for samples low m organics) or by applying sample cleanup (for samples high in organics). Of course, cleanup techniques wer* not available for the benzltflncs/semldines, so the options were limited for this analysis.
A. METMOOS FOR OICN.ORQAhll.INC WASTE PVPOLTSIS PR00UCTS
Methods 1-4 detailed below were applied to the bench seal* burn products. Not all methods were eppl led to all samples! appropriate methods were chosen for each sample according to the overall concentrations of organics tne sample, as welt as the analyte concentrations.
in
MOMS 220S10
DSOlt/i$H
KETMOO i, GENCRAL extraction NETmOO EOR TETRACHlOROPHENAZINCS ANO TETRACMLOflOBE N2101NE 5/T TRACHLOROSE H101K 5
i. Place about O.S g of sample In a 14 at Pierce vial.
2 SrH( with! a. Pyrene-dlO - 2,0 ug/g to. Chrysene*dl2 * ?,0 ug/g
3. Add 5 t of benzene.
A. Extract by ultrasound for 30 minutes.
KUK 2. EXTRACTION NCTHOO FOR T TRAC MLOROPHCNA2 INC SAMPLES REQUIRING SPECIAL CLEANUP fOR LONER DETECTION UNITS
1. Place about a one gran sample into a 40 at Pierce vial.
2. Dry sample If needed by adding about t gran of sodlux sulfate tc vial.
3. Extract sample with three IS at aliquots of methylene chloride.
4. Confine extracts In a I2S at separatory ftsvsei and add 40 at of 101 hydrochloric acid, remove add then add same awxnt of I n potasstj* hydroxide and remove base.
5. Add 10 at of hexane.
6. Drain Into a SO at cantrlfuge tube and reduce volume to I or 2 at.
?. Quantitatively transfer sample to coluan containing } grams of silica gel and I centimeter of sodlue sulfate on top.
B. Elute with 30 at of hexane first and save.
9. Elute with 30 al of methylene chi or IOe/hexane and reduce to I at.
10. Elute with 40 ml of 101 methylene mcetate/hexana and save.
MOMS
220811
METMOO 3. SOXHlCT EXTRACTION METHOD fOd TETRACML0R0PHCNA2INCS. TeTRACMLOROeCNZIOINES/TETRACHLOROSCHIOlKS. PCB'S, TCDO'S ANO TCOf'S - USEO TOR "CLEAN* SAMPLES
1. Place about S.00 g of *arrie on four centimeter* of odltx* tulfate in a SoxMet extraction apparatus (without thieble).
2. Spike wlthi a. Pyrene-dlO - 0.20 ug/g b. Chryene-dl2 - 0,20 ug/g c. 3,3*,A,4'-Tetrachlorot>lphehyl-o6 - 0.20 ug/g 0, C13-TCDO - S.39 ng/g e. CI3-TC0f - 4.ST ng/g
3. Place four centimeter* of looljn tulfate on too of the sarrele, 4. Add 300 nt of methylene chloride, 5. Extract for 40 hour*. 6. Concentrate to I mL by using Kuderna-Oanl*h aooaratut followed by
nitrogen blowdown.
AETHOO 4, EXTRACTION NETHOO fOR PCB'S. TCOO'S. ANO TCOf'S - SAMPLES REQUIRING EXTENSIVE CLEAN UP
1. Place about S.00 g of sample into a 40 at Pierce vial. 2. Spike wtthi
a. J.3',4.4'-TetracMrod1Phenyl-dfc - 0.2 ug/g b. CIJ-TC00 * 5.14 ng/g c. CII-TCOf - 5.03 ng/g 3. Extract by ultrasound with six 10 at aliquot* Of benzene <15 minute*/ extraction). 4. Elute extract* through a 10 at di*po pipet with gla** wool plug. 5. Rinse sample with 10 at of methylene chloride and combine with benzene extract*.
6. Extract by ultrasound with four 10 at aliquots of benzene (IS minutes/
extraction). T. Reduce extract volume to 10 at and wash with ?$l sulfuric acid.
HONS 220812
I cmISOOKM SULfATE
i t *i ------- 1 t
!
'____ 4 cn PERMANGANATE SILICA GEL ____ ___ I ca SILICA GEL
i Ii ________ 4 ca ACIO SILICA GEL _________ I ca SILICA GEL
I --- I
\**/ \/
.________ 4 c BASE SILICA GEL ______ GLASS WOOL PLUG
10 ca 0Ipo Pipette
6 CA ALUMINA FRACTIONATION GEL (OojIc)
\x/ \/
CLASS WOOL PLUG
B. Reduce extract volme to dryne, dilute with to *L of hexane, and Quantitatively tranfer to cleanup colmn.
9. Cute extract through doth cleanup and elmtna colmns with 40 me of hexane,
10. Elute aiinlna coltam with IS nL of St methylene chloride/hexane.
11. Cute aliMina col inn again with ?0 at of SOt methylene chi or I de/hexane,
i?. Collect each eluent and concentrate to I ml ualng nitrogen eiowdown.
NEWS 220813
8. METHOOS fOR OICMLOROANILINE WASTES Method* S-6 detailed below were applied to analytl* of the dichioroonlIIne watte* uted at starting material* In the pyroiytl* studies. Method S. ettentiaily a tample dilution, wat uted for the tetrachlorophenailne and tetrachlorotemidine/benzIdine anaiyt't. Method $ wat the extraction and tampie cleanup method employed for the PCB. TCOO, and TCDF analyte*.
METHOO 5. SAMPLE PREPARATION fOR TETRACMLOROPtCNAZlNE AMO TETRACHL0R98ENZlOlKE/TtTRACMLOROSEMlOlME ANALTSIS
I. Place about C.l g sample In a H "t Pierce vial. Z. Add 10 "t benzene and shake vigorously. ). Ollute the resulting solution iilO in benzene.
HONS 220814
P50II7:$H
METHOD 6. EXTRACTION NETHOO fOR PC8'S. TCOO'5 ANO TCDF'S
1. Place about 5.00 g of sample into * <0 N. Pierce vial. 2. Spike with:
a. 3,3',4,4'-Tetrachiorobiphenyl-d6 * 0.2 ug/g t>. CI3-TCOO - 4.8 ng/g. C. CI3-TC0P - 4.7 ng/g. 3. Extract by ultrasound for 30 minute* with 20 *t benzene, 4. Shake with 10 nt St sulfur Ic add. 5. QuantitattveIy transfer sample with benzene to a S00 "1 bottle. 6. wash extract with SO at 501 sulfuric acid and remove add. 7. Raise benzene level to 200-250 . 8. Hash with 801 sulfuric acid u/stti dear (8-8 washes reouired). 9. Hash with 40 at concentrated sulfuric acid. 10. Hash extract with SO at water followed by 201 KOH followed by SO at water and remove water completely. 11. Reduce volume with Kuderna-Oanish to 3-5 at, 12. Reduce extract volume to dryness, dilute with 10 at. of hexane, and quantitatively transfer to cleanup column.
MOHS 220815
........... :
................................... 1 C* SOOIUM SWLfATt
: ........... :
................................... 4 cm tl POTASSIUM PtRMAKAOAKATt SILICA CtL ................................... I cm SIUCA GU
: ........... ..
...................................... 4 cm ACID SILICA GtL ................................... I cm SILICA GCL
: ................................... 4 cm 6ASC SIUCA GtL
'./ \/
............................... glass wool plug
1) flute Mmole through c<ehuo colvrtn with 40 ML hexene eng collect In SO-mL centrifuge tub*.
14. Concentrate to 1.0 *t In warm #V3 bath under gentle Stream of nitrogen.
HONS 220016
osoimsn
GC/nS ANALTSIS
Sample extract* were analyzed for tctrochlorophenay'net, tetraehiorutemldlhe:/ tetrechiorobenzidinet. and PC8* utlng the instrument condition* outlined in Table* 2 ano 3. For tetrachlorophenezln** and tetracMoroOenz Idinet/ temidine*. potltlve* were IdentlFled try concurrence and correct ratio of the major ion peak*. Standard* containing one Itomer of tetracnlorgpnenazine and one (toner of tetreeMorobenlldlne were uted to calculate retoonte Factor* bated on the major ion area* For tnete compound* relative to tne internal itanoord area. The** retponte factor* were uted to calculate concentration* of an ooiitivc* detected In tne extract*. Tnlt approach attune* identical matt spectral retoonte for all Itomer*, an assumption *rftlch give* accuracies within 301 For molt compound*. For tne PC8 analysis, a ttenderd containing from one to three I toner* for each chlorine ciatt * analyzed to determine retponte factor* for eacn datt (mono- through deca-l. Tne complexity of the PC8 data (due to the large fHmcxr of peak* pretent in many of the extract*) necettlteted that tne data reduction scheme be tlmpler than the peak-try-peak approach taken for the other analyte*, a* a result, an approach bated on tutting the tote! area* for PC8* of each chlorine ciatt mat adopted. Octet!* of thi* procedure are given In Table 4.
MOMS 220817
RS0M7iSN {
TA8LE
NUHBtft or ISOMERS FOR EACH ANALYTE CLASS FOR BENCH SCALE OCA PyPOLTSIS
compouno
Tetraehi orophenerlnes TetracMorooeni Idlnes/semldlnes tCODs TCOr* PCBs
O
h>
II SOMERS
22
22 38 209
PER ISOMER REQUESTED DETECTION LIMIT (ug/g)
0.048 0.001S 0,046 0.026 0.0048
Breakdown of PC8s For each chlorine class:
COMPOUND
fISOMERS
MonoeM or ot 1 pheny 1 * OlchloroOlpheny1 TrIchloroOlphenyls Tetr*Ch)OrotlpT'Pyl Re n t ac h 1 or o<> 1 (N>ny 1 He *ac h 1 or ot> 1 pneny 1 wept ac h l or ot> I pneny 1 Oc t ac M o r CO 1 pt>eny 1 Monaco1oroO1pOenyI Decachl or ot> tpoeny 1
total
3 12 24 42 46 42 24 12
3 I
209
MOMS 220818
NS0lt7i$M
table l, GC/HS COhOITIOMS for bemch SCALE BURN ANALtSES
Inttri/nent: Column i
Temperature program : Injector temperatures Transfer line temperature: Inject Ion mode: Ion source temperature: Hats spectrometer mooe: Ions monitored:
Internal standard!
HP 59BSA OC/HS system with SIDS software ano T9?0 disc di Ke For oate storage
30m Fused Silica Capillary coiom coated with OB-S 1lould phase (JiW) - connected d'rectly to source
hold at SO C For 4 min.; program at 8 C/mln to 300 C; hold For duration oF run
?S0 C
?S0 C
spl111ess
?00 c
selected Ion monitoring
tetrachiorophenazlne: 3t6.3IB,3?0.?B3 tetrechtorobenztdtne/tamldine: 3?0.3??.
?S0.?S? RGBs: see Table 3
anthracene-dlO
moms 22019
tS0H7:5H
TABLE 3. IONS MOHITOREO FOR PC8 ANALYSIS
Chlorine Cl*}}
Honoch1 or00>phenyl DtenloroO'phenyl Tr1 chi or00Ipheny1 Tetracnloroolphenyl Pent*Chior001oheny1 Mf**Chlor001Ohenyt Heplc h 1 or oO 1 pheny I Oc t ach 1 oroO 1 pheny 1 NonacMoroO Ipheny 1 Oec oc h 1 or oOl Phenyl
h*JOr Ion}
IBS.IBB H2.2U *SS.9^$7.9 289,8 - 291.8 323 e.m.a 3S7.B.JS9.8 391.7.393.7 4?7.7.4*9.7 481.6,46}.6 497.6.499.6
MONS 220820
JS0117 tSd
TABLE 4. OATA REOUCTION PROCEDURE FOR PC8 ANALYSIS
I. Obtain total loo ore* and matt toectrum For each ixejor peak lo th* extract.
2. Examine each matt iPfCt^to ano determine whether It l a PC6 o'" an loterfereot.
), If the matt toectru* It PC, determine which chlorine clatt (aono-.dl-.trl-.etcl.
4. Add total loo areat of PCBt of each chlorine c'*t* (e.g. total trfchlorobiohenyl areal.
S. Divide total area by retoonte factor for that chlorine clatt to obtain concentratIon In extract.
4. Calculate tempi* concentration.
MOMS 220821
K501I7:SH
RESULTS AND DISCUSSION
A, PrPOLTSIS PROOUCTS
Result* for tetreehtorophenezlne end benztdlne/semldlnet In the OCA pyrolysis product* are presented in Tablet S - 7. Table S gives result* oota>ned using the NetrxJ I (simple screening extraction) workup procedure. Detolte me high detection limit* inherent in this method, a rvmoer of samples were sna'vjaole using this procedure, In cote* where the Phenazine ano benzidine/ st^uoine were not detected In this analysis. two courses of action were available. If the particular sample was low In organic content, as indicated bv a relatively clear colorless extract. the sample was subjected to Soxhlet ovation {Method 3>. Thi* was the method of choice because it permitted simultaneous extraction of all analytes retired for this study, Including pffls, TCODs, and TCDf*. and because this method permitted the lowest detection limits. Results from this extraction are given in Table 7. if tne sample a% high in organic content, at indicated by a highly colored extract from "r?'*od I, the extract was cleaned up using Method 2. This allowed lower detection limits to be achieved for the tetrachloropnenazines, but did not permit analysis of the terachlorobenzidines/temidinet. Due to financial consideration*, development of cleanup procedures for these compounds at not oesired by MIC at this time. Results stemming from the Method 2 cleanup erf given in Table
Pee results for the OCA pyrolysis products are tabulated by chlorine class in Table 6. These results were obtained using extracts resulting from Method 3 (samples low In organics) or Method 4 (samples high in organics), it should be noted that the final alumina coliatn fractionation In Method 4 was designed to separate the PCOs (51 CH2Cl2/h#xena eluant) from the nonretalned organics (nexane eluant) and the TCDOs/TCOfs (3(71 CM?Cl?fhexane eluant), While this procedure sucassfgily Isolated the TCOOt/TCDfs in the $01 CKTCli/hexane fraction, the PC8* were found to be spread across all three fractions, hence, all three were anaiyzed and thair results summed to give tne concen trations in Tab I a 0, Tha method was subsequently modified for the OCA waste extractions.
HONS 220822
B. OICHIOROANILINC WASTES
Becau*e all the dlchloroanl i me wattes were similar in organic content. tangle preparation procedure* were more uniform than wat the cate with the pyro'ytl* proOvc11> Petultt of thete analyte* are 'jlven in Table* 9*11, Table 9 lists retults of the analytet of Nethod S extracts for tetrachlorophenazinet and tetrachlorooenxidlnet/temldines. Table 10 give* result* of anaiytl* of method 6 extract* for PCBt. and Table M provide* recoveries of native tolke* for the PCB analysis. Note that while not reaueited. the NIdland-Pot* 0C* watte tample wat Included In the PCB anaiyii* for comparison purpose*.
Detection limit* given In the*e table* are generally higher than the reouejted I ppm total Isomer content limit. This I* due to limited sample tie. cleanup limitation*, and the large fsmfcer of isomer* analyled. however, ir, nott ease* thl* proved to be Irrelevant tlnce analyse* were detected in the samples above the reqye*ted level of detection.
MOWS 220823
tuit >- inunmoruMnn * TmuDeiobOiuiibmt/TiiuoiioeonNibiHi iimn ft* aumi'KAir mourn ur.ru i M;ra>u> on*; ctauv tiiumn mtmo (nithoo I)
JJUffLl 1DLM1i HOT10* |Jich IS Mich 4S*4 coapoiitt
utu ?_ (i) 0.411
o.sii
fiuu uiun JSy (-1
t.
s
tiuniM J4CT04 1 1 10
-
WUt oaimAi i m Of 1S4VUO&
muCHjoeoiunibiii/ trTMCIOMW|Du;il1 jirMCt*oicnoiii 21 l HO*
4 4 > HO*
_ Krovtat
ftlDiHIO CMifsur-aio 4 * 4? 1 44 5 51 4
IttCh 1>, 14 co*ro*itt .its
so .
1:10
1.4 10*
).) I It1
121 111
MlCh 14 itch 1 cot|mi
o.osi 0 410
s.t s.o
1:10 1:10
241 HO* NO L4*t fbl 41 HO*
40 4 S) * 111 101
Mich 1* KA
0.4*1
s
-
MO J4tt Table 4] HO*
1 11 1)1
leh 17. 14 eMfonu * 141 KA
S0
] ! 100 lf.hrnat .or! 1 10 Ibem idtne i
1 1 * 10*
1 J 10*
M 5 145
itch 20 KA
0 sso
s.o
*
H0 Itee Teble 1) NO I4ee Table li
*} *
*7 0
Mich }0 KA duplJcti* . S41
S.O
*
HO l*ee Table H HD lOer Table 1|
41 1
M
Mich 21 KA
,*01
s.
-
NO JSee Table 1l HD lOee Table 1i
>4.0
4 4
KilM Hint
* s.o
-
HD
HD
Ilf III
So MOt ilLa4 OfltCllH Halt * 100 *g/f ( eech leaver, or 44 )/( (or thr epproiiaaiely 4S0 liotMi
*M0 Ml 4lt#Cltd. ilMIlM Halt mi 1* a*/* far each laeeer, or 4 S i*/* (or the approilaately 450 tiwri
MOMS 220024
TAPLf .
TtTtUCHbOKOrMrHAKHE MSULTS TO* CHCH-fCAU' MMOLTSI* SWirLTS WOUIAIHC SriCIALIltD CITAK I.'I rOI> IMl* OtTLCTlOM LIMITS (NETmOO II
TWIILT lOCHTiriCAllDM etch 1. T cob*o*lt* etch 1, * cMfeillr <
lev ri>r-r^ etch IT etch IT duplicate
m () 1 (111 i.*m
1. MSI l. ITS?
riWL eTMCT votive i*d
c0 i0
oiumoN *ACTO*
-
-
1 . 1 -
total (wc ot isorurs TrTiorHLf'ofNrM:ir _ 1*9/9)
ne*
>)
\ VfOvlM Tl lMCNLO0OrHtNAIlHt
* ns
MO* MO*
*ND noi diiKltd Drtectlen libit ItQbcrt.
1
for orh inti, or t lotil el )}
*lov iplti l.(< if/| |i|,l,l>tiirichlore|>hcMtiM
ter the M el th* li peetiblr
NONS 220025
TAKU 1
niHACMU>OrHfNAl!NE AMO TtTAACHU>AOIIMir[HNr/MTAACHLOAO$LMIOINr ArtUI TS COM |rNCH-$C*lS HAOLTSIS (AMrUS AAt A* AID USIWC tOAMLTI tuTAATUO* fA U3WI A mfTlOH LIMITS (Ml TMOD M
writ lAuniriCAtiOM tilth I Mu A II toleh 21 tuflic.tA
LwOVI
IMI i.l>
IIUI CJTUC1 JWUXI {*1
1.0
t0
1.0
6U 106 JtfTv*
-
.
toi 6i __ or
ret 660640QPHIM62IM 0 it 0.*J J 0.0*0
1! si
iiiuctyMumom/ jttuauwvriiot
n>*
FD* HD1
_ 1 I ti t) r
Mimt 2ro our$t*e-410
m 122 it
221 III *1 1
Ki not Mt*ct*d. tot Action iir.it tu .0t .*/* p*r iterate, or I*
for tht Appro.lottrir ts ioomii
MOWS 220626
TruMLiTr
utuLU or qc/ms waists or hlnch-s<-ai DlCMLOHOANlUNt PTBOLVSL4 BBOOUCTS roo roiTCHi/i* NATt 0 B t P trcnai (MTTttOft 1 ft* HCTHOD 41
conrounp
datv* 4.s .4
BATCH M
*ATC* 1 KM
TOTAL CONCf HTKAT 10H ua/jt
BATCH IS
BATCH 17,11
BATCH 14
BATCH 20
BAT\ H 2)
Cl 1 -biphanyla Cl,-blrhenyle Cl ,-bipheny 11 Cl ,-biphenyli Cl,-biphenyla Cl,-blphenyl Cl .-blphanyl1 Clt -blphtnyll Cl* -blphanyl Clit-blpbonyla
o 002 0,0; 0 0* 0 os 0 01 ND HD HD HO HD
0.14 0 *4 0.4J 1.40 0M HD HD HD HD HD
0 1J J s* i *0 4 01 f 04
SO HD HD HD HD
0 04 1 SO 1 14 4.11 ll 41 HD HD HD HD HD
0.01 4* 0*41 1 0* HD HD HD HD HD HD
0 04 0 S? 0 24 02 HD HD HD HD
HD HD
0 4S " 0 01
HD HDb HO HO HD Ml' ND HD
0 0) 0 ot ND
0 0L HD ND ND NO ND
Total PC*a
0 11
9 bacovtty
l.r ,... ` -tat r Chioroblphtny1-d.
122.4
1.12 114.0
24.1J 420.1*
20.11 140 S*
2.40 104.0*
0 44 74 . 1
0 44 jpi 4
0 07 ft 4
*apparent tilfh recovery .tault of Inttrlarenca at retention tioc of druteiated apihe eooeouftd.
k*i not detrclad. with * datoction liit or Ml *9/9 per PC* itawi for iti^lri contalnmy iaa* than s ,9/9 total
hCta nd e.l af/f par K1 lioaii (or aaaplea containind oort than 9 09/9 total PCde. To deterolat th* detection 11*11 (or aich ehlorlo* elaat, oulllply thr par 1KW r da tact Ion lialt by tht auoter of Uonera la that claaa
(Tabl* II.
MOMS 220*27
USO117iSN
table 9
RESULTS Of GC/NS ANALYSIS Of OICMLOROANIUNE WASTES fOR TETRACMLOROPHENADINES AND TETRACML0R06EN? InOINf S/TE TRACmlOROSEHIC lNES (NETnOO S)
SAMPLE 1 DENT if ICATION
pc a Residue OCA Heeds OLA Residue - a OCA Residue - B OCA Residue - 6 (duel Blnk
total CONCENTRATION of ISONERS
TETRACMLOfiOPHENAZlNE
TETRACHLOROBENZIDINE/ TETRACHLOROSEMIOInE
6.7 0.91 NO NO 4.7 zs.o 4.4 JS 0 4.7 40.0 NO NO
no not detected. with t detection Unit of I *g/g per Iscmer. or 22 g/g for the 22 tetrochloropnenaz Ine Iscrar* end 6S0 mg/g for the oooroxIrately 6S0 tetr*chlorotnzIdlne/tenldlne Isomers.
MOMS 220*28
tm>u io. MSULTt or GC/KS MtALTSC* Of OlCMLOSOMIlUItt KASTIE TO* POLTOlLO* 1NATMJ DlfMCMTLf <rc*H INI THOO il
tOWI-CVTtO Cl-b* fKt ny1 C)|4biphiAjflt ci|4blptMAjrl> Cl,-blphtnyl Cl a*bibhnjrl Cl f'btplMAjfll Cl |-bipriftjrl8 C)f-biphtnylft Clf^blphcnyli ChfblplMnirli
-- ' A
SVU'U 0 10 1 ft 0 17
4.7ft NO NO NO
NO NO HO
SAHfLf nu* 1 12 0 01 SU NO NO NO NO HD NO
TOT At l CMC. INTUITION <.J/))
` * ft
SUU'LT
wr*
tC A
OUr**!CATE HI A1S ftl S IDul
HO no ft 4ft
0 **
0 4
2 1
0 11 NO *11
10,*
NO 1.V4
NO NO NO
NO NO NO NO NO HO
no NO NO
MD NO NO NO NO NO
N| THOO OI>Npt
NO HO NO HO HD HO HD NO NO HD
Tvt8l Kli
l htrovtry 1,1.*,* utrachlorobi phenyl 4.
*.*4
i.H
*.
*0.1
11*4
0 4*
4 *4
iti.i
4J.4
1* *
ND 10,*
M( ''t S s**n
HO 0 44 0 11 * (4
NO NO HO HO NO NO
4 71
11 1
*00 l 4*t*ct*4, nit* OttKilw Halt of 01 ></* par PC * torn* r To OnrniM t hr daloction I ton for itcK chlorlM cloo*. Pultlplr thf p*l looon 4*tction libit by tht iwtar Of imtgi in that cl*M ( Tab)* I )
MOMS 220829
C50ll7i$n
TA8lE ||. SPIKE RECOVERIES FOR NATIVE PC8S IN DICHLOROANIlINC WASTE
CONPOUND C I I -b lDHffny I v
C I2*biooeny l * Cl 3-E>i teeny's
C l 4-bl0tieny I j
C 15*01 tVieny I
Ci6-blbhenyls Cl 7-blOhenyl t C l8-0l(*>eny I* Ci9-blohenylt C110-01phenyl
X RECOVERY
A SanpvE LOW SPIKE <0.2 ug/gl
A 5AhPlE HIGH SPIKE (0.4 uq/q)
55,7 107. 1 67.1
69.3 120.6
61.7 69. 7 91.6
85.0 86.4 89.2
89.9 68.6 66.0
92.5 95.0
93.4
106.7
102.7
85.4
19.0 S7.3 35.7
S7.| 120. 7
73.7 77.6 62.8
87.5 61.3 95.4
89.5 91. i 96.7
92-6 88.1
85-2
81.9
86.6
77.3
I,J`, 4,4' -Tetr*ch I or obi atony It *06
65.6
0 Hitt X recovery for each Itooer tptkeo Into the watte.
90.3
MOMS 220830
ANALYSES rod:
"TCDDs TCOf
NONS 220831
RESULTS roa afcfcCH' scale burn PROJECT FOR tcod-s and tcof;*
Following completion of the target compound analyst % the
samples were submitted for TCOD and TCDF analysis.
Tne sanples
were subjected to further cleanup prior to their analyst* t>y
GC/ms.
Tne samples had initially been spued with 2.3,7.e-TCDD
and
2,3.7.8-TCDF before the start of sample preparation.
Initially
the further cleanup Involveda solvent exchange to
hexane, Tne Batch 20 and Batch 21 samples were then subjected to
successive washes with water, concentated sulfuric acid (until
the acid layer was clear), water, 20% potassium hyc-c*tac and
wat t?r .
Tne hexane from Botches 20 ond 21 was then concentrated. d< icd and
applied to the head of a mixed phase column consisting of (top to
bottom) 2 g of silica. 4 g of sltlca plus 40t Sulfuric add. I g
of silica. 2 g of silica pius 36% potassium hydioxide and i g of
si 1 lea.
Tne column was eluted with 50 mL of nexa'-e ar.d the
eluent was collected and concentrated to 2 mL.
The he*ant- was
tr.en applied to a column consisting of 2.5 g o' Woe`m Ba\ ic
alumina.
The alumina was eluted first with ID
of 0 2%
methylene
chloride In hexane solution and this act ion
was
discarded.An additional elution wasmade with 15 r_ o'
50%
methylene chloride to elute the TCODs and TCQFs frem the column.
This fraction was then concentrated to less than j mL ana
subjected to further cleanup by the EPA Option 0 technique along
with the remainder of the samples.
The Option 0 technique Involves placing the sample or the head of
a co1umn-contalnlng IB% Carbopack C on Cellte packed to a depth
of 2 cm In a 1.0 cm 1.0. plpet. The column was then eluted with
l mL of hexane, I mL of a 1U cyclohexane* methylene chio-lde
mixture. 1 mL of 7$i20>5 methylene chloride*, methanol* benzene
and finally 2 mt of toluene.
The toluene fraction had 50 ul of
dodecane added to It and was concentrated for analysis.
Tne GC/nS analyses were conducted using a Hew Iett/Packard *987
GC/H& instrument.
A 30 n OB'S capillary column was used for the
TCOD analyses.
A 60 m SP2330 capillary column was used for the
TCOf and 2,3.7.0-fCOF specific analytes.
The mass spectrometer
was operated In the selected Ion monitoring mode analyzing for
Ions characterl*tlc of native (unlabeted) TCD0 (m/z 257, 320.
322). C-13 labeled 2,3.7.8-TCOO (m/z 334), native TCOf (m/z 241,
304. 306). C-13 labeled 2.3,7,8-TCDr (m/z 318), and pentachioro-
and haicachloro dfphenylethers (m/z 342. 376).
The results of the analyses are shown In Table I.
Table 1 also
shows all pertinent QA/QC data. PI case note that It Is Incorrect
to calculate spike recoveries for internal standard calculated
results as the Internal standard corrects for recovery problems
due to losses In workup.
I RONS 220832
Table I'. , Sample
Results iof jAnalysIs for TCOO* and TCDFs
TCDO
2378TCDD added
TCDF
2378-
TC0F
added
Batch 4,5.6 Composite ND<7.9) NO (7.8) -
Batch 8.9 Composite ND(4.6) NO < 4.6) Batch 13.14 Composite nD(O.S) ND < 0.5)
-
Batch t5
ND(1.2) ND(l.2) -
Batch 17,(8 Composite ND(1.4) ND(1.41 -
Batch (8
NO( 1 . I ) ND<I.1) -
Composite spike 1 (Calculated Levels)
-
--
Composite spike l
- 4. I 4.4
Composite spike 2 (Calculated levels)
-
--
Composite spike 2
-
7.8
4,5
Batch 20
N0(1.6) N0(1.6) -
Batch 20 High Spike
-
17
19
Batch 21
ND<I.B) ND(1.8) -
Batch 21 Low Spike
-
2.6
2.0
A-sample
N0(6.6) no<o.n -
A-tampie Low Spike
-
3.7
4.2
A-sample Htph Spike
-
8.0
9. 1
8-sample
N0<2.6> N0(0.1) -
B-sample Duplicate
ND(1.6) ND(0.1t -
DCA Heads
NO(2.3) ND(0.1) -
PCa Residue
NO(I.O) N0(0.1) -
Method Blank
ND(18) ND<1.0) -
N*D< ) Not detected (detection 1Imlt)
NO< 7.8) NO(0. I) -
6.3
0.9
-
71
10.3
-
30
5.8
-
6. I
1.6
-
ND(0.8) n0(C.Ij -
8. S 1 .4 -
9.7 5.0
1 .4 4.C 1 .d -
17.3
1 .6 4 , t
NO(I,6 J ND(1.Ci -
-
)9.4
19
NO(0.6) NO ( 0,5) -
- 1 . 1 2.2
20.8
9.2
-
-
(3.1
4.3
-
IB.6
9.4
20.4
8.8
-
20.0
8.7
-
nD(0.6) N0(0.1) -
11.8
1 .6
-
ND(2.4) ND(0.|) -
MOWS 220833
i
Monsanto
MONSANTO COMPANY / DAYTON LABORATORY / DAYTON. OHIO 4W07
_
ESC/DAWON_
____
U>ep*rtjent/seciion j
__
ANALYT^AL . _ (Type of Report)-
.
REPORT HO. : V- 91 9 i; ddi r. C. -* ;
JOB 'PROJECT NO, IE-.' , Id 0
DATE
-s; ) 9 o i
PERIOD COVERED.
TITLE
-i SIS C* Cl t \j: S
AUTHORS S
RECEIVED I
#16161984
OhRANTO CO>**"T
vna
***
T LOUli
; pypoi'isis
T IT L E :
>
L*l k^I ci. *<(/.
ADSTRACT-
Tlu offgas frc- the Ler.ch-scaJe F;rc)\$;s cf
\ v aste v.as a-,al_, rc-c for total tctricMc ro-
;-.lt< j nos . 7 hr rts-lts of those analyses art
show-,
this rei-ort,
technical app?o\a::
-'.`J), Brooks Senior Pescarch Crooj Leader
APPROVED BY:
. ..
R. P. Ivory Environmental Sciences Center Service Project Manager
APPROVAL DATE:
7/- tj
PXSTfUCTED DISTRIBUTION: (see over)
COMPANY CONFIDENTIAL
This 4oomM ti ths props rty of Monsanto Csapany and th* roc Ipitnt is roapooaihla for its safekeeping and disposition! It eonto ins CCMPlDOniAL WPOMUTIOM ufelch aust not lx reproduced, rovsalod to e>*utherlced parsons or oont outs ids Monsanto Ceepany without propsr authorisation,
MOWS 22O834
DISTRIBUTION
COPY NUMBER
1. D. hclsal 1
2. R. F. Ivory
K2B 1250
3. S. L. Mazer
1250
4 . Central files
1250
5. Technical Reports Library R2C
ABSTRACT ONLY H. A. Koltermann
SOIL:
Distribution of this report is restricted. Requests for additional copies should be made through the principal contact at the Monsanto location involved or the Manager, Environmental Sciences Center, Dayton Laboratory, Dayton, Ohio.
AC KSOVOE DGEKENT
Contributions of the following Dayton Laboratory personnel to this project are gratefully acknowledged:
Analyses: s. L. Mazer
at*** tci
COMPANY CONFIDENTIAL
MOWS 220835
aAOi!7! in
I.INTRODUCTION The offgas from bench-seal e pyrolysis of a dichioroenii Ine watte wat collected by NIC personnel to a ter let of Imp Insert, and the Impl nger contents and associated sampling apparatus were submitted to the Dayton Laboratory for GC/hs analyses for total tetrachiorophenezines. This report details methods for and results of these analyses.
it. sample preparation hetmoos
Table I lists the samples received and Quality control samples prepared in conjunction with these analyses. Tn native spike samples were designed ta demonstrate that the tetrachiorophenezines "ere recovered from each matr Ik. and the blanks were analyzed to show that the samples did not become contaminated during sample workup.
i samples for this study fell basically Into three categories: a. water samples, including HCI and NaOH solutions. b. Apparatus samples. Including the gas washing bottles and Teflon tubing connector. c. Crystals scraped from inside a pipe (Batch 22 scrapings).
The sample preparation methods designed for each category are described be low.
MOMS 220636
hETHOO I. EXTRACTION Of HATER SAMPLES
1. Place 2S0 ml sample Into separatory funnel. 2. Spike with I ug 3.}',4,4`-tetrachloroblphenyl>d6 surrogate spike compound. J. Extract with one 90 and two GO-at portions of methylene chloride. 4. Dry extract Oh SOOil/n sulfate column. 5. Concentrate extract to I ml, Exceotioni MCI trap solution extract was
concentrated to IS i.
METHOD 2. EXTRACTION Of GLASSWARE AND TUBING FROM SAMPLING APPARATUS
1. Spike apparatus with I ug 3,3* ,4.4'.-tetrachloroblphenyi-d6. 2. Rinse sample out of apparatus with I SO - 1000 ml methylene chloride,
until crystals are entirely dissolved. Exception: Dissolving of crystals In hci gas washing dottle was aided by addition of 200 - 300 ml distilled deionized water. This water was then extracted with methylene chloride. 3. If water was used In washing out crystals, dry extract with soditx* sulfate. 4. Concentrate extract to 1.0 ml. Exception: Extract of Ki gas washing bottle was concantrattd to 20 al.
HETHOO 3. SAMPLE PREPARATION HEtHOO FOR BATCH 22 SCRAPINGS
1. Heigh 0,1 g sample Into 10 - ml volumetric flask, 2. Dilute to mark with methylene chloride. 3. Prepare a It 10 dilution of the above solution In Methylene chloride.
HOMS 220837
ACO11
111. GC/RS ANALYSIS
Sample extract* were #na'v^eo for tetrachtorophena2incs using the instri^ent conditions outlined in Table 2, Positive* were Identified by concurrence and correct ratio of tne najor ton peak*. Standard* of I.2.S.T-tetrechloropr<enailne were wed to calibrate, and all re*oone* were normalized to the internal itanoaro. Recoveries of the deyterated sPlke ano of the native rt'acnioropnenaztne were calculated relative to standard* simulating loot
- jvfr v ,
IV. RESULTS ANO OISCUSSION
Resu't* of tne GC/RS analyse*, given In Table 3. show that the majority of tne tetrachloropnena;Ine was found In the NCI gat washing bottle and it* content*. Recoveries of the 3.3*.s.s'-tetrachlorobiphenyi-oS indicate that good extraction efflclence* were maintained for the analysis In general, and recoveries of the native terachiorophenazine spiked into each sample natrl* snow that these compound* in particular were well recovered. The method blanks furthermore Indicate that good laboratory techniques prevented sample cross'contarrilnation. A Sixwka'y of the offgas results Is given In Table 4.
MOMS 220838
AOOIDiSK
table I. SAMPLES PREPARED and ANALTZEO fOR OCA PrROlYSIS OffGAS STUOY
SAMPLE IDtNTIfICATION
MIC SAMPLE
<*. nCl Trap Solution C 41 MCI Blank Oayton tab 1 HCi Blank Oavton tao 41 hcl * ug/L phenezine tpike
101 NaOH Trap Solution MIC 101 NaOH Blank Dayton lab 101 NaOH Blank Oavton Lab 101 MOM 4 yg/l phenazlne *plk*
'jat Washing Bottle \a>i Gas washing Bottle Glassware Blank Glassware * l ug phenazlne spike
MIC Teflon TubIno
Dayton Lab Teflon Tubing I U0 phenazlne tplke
Batch 22 Scrapings Batch 22 Scrapings (duplicate)
QC SAMPLE
HOMS 220839
-V
Atoimsn
table 2. GC/HS CONDITIONS FOR BENCH SCALE BURN ANALYSES
Ir-s*. ri/nent: Column:
Temperature program s
Injector temper*ture: Transfer line temperature
lectIon node: Ion source temperature: Mass spectrometer model loos monitored) Intern*! standard:
HP S9BSA CC/NS system ultn BIOS soft-are and 7920 disc drive for data storage
30m fused silica capillary column coated with DB-S Mould Phase (JIM) - connected directly to source
hold at SO C for 4 min.i program at B C/mln. to 300 Ct hold for duration of run.
2S0 C
2S0 C
solltess
200 C
selected ton monitoring
tetrachlorophenazine* 3lS.3lB.320.2B3
anthracene~dlO
MOMS 220840
tajLf ), Mtuirs or cc/nt akalvsis or orrcxt luvixi ro TCTRACMLOnon
nit
t NCI TOP Solution
NIC tt MCI Hank Dtpton Lab it NCI llanl
Myton ut It MCI *4 vg/U phtn*H i|<Ue
tot MtOM Trip folutlon
*" XcUKAiBiavlUMiinci ml
t.ll a 10* MV* MO *
11.0
MIC 111 MOM ilont
MO
Oayton Lib 101 NiOM Hint
MO
Dayton lab iOt NaOM i af/L phenetlne tplkt
-
NCI Cat Mithit>9 bottli
7.II 1 10*
MiOM Cat Huhi 119 bottli
li.l
kd
CUiavire 1 >1 pheninnt apik*
MIC Tirton toblnt
* l.Jl
btytoi lab tiflon TubInf tl if pheniilna iplki
batch 1) bcnpinfi batch It icriplnfi Uupllcitil
tit i4
_,
___
* MCpVtY_
7 If<rKhl*C*i*Pf|lf
l.r.t.f. litN'OtWPObimfiTi-c*
MS* M0b
MS 1)7.1
NS llt.O
ItO.t 111 7
Nf W w lit,7
HI 111.1 ttl.l lit 7
m MO
ns 117,1
MS 1*1.7
.0 Ml 17.1
t.l III.* 74. t
Rl Mk m HA
* not tplkid with aitivi titrichlorophanatlna. bMQ not quiitifiod. Staple wi too high in ort*nic* to bo concentrated to i ot, to epiko couU not bo enalyttd,
eMD not batoctid, Kith detection iiait ot 1.1 *9 per tatrathlorphinatint Ihhi, or 1.4 *9 tot the totoi ot lit It i hMA - not applicabla. sons'll hi diluted rottwr Ua> attracted, no ipikin* mo not MCttMry.
iWU UK WIWtM l'lt-04 I9-li. l-*t-*7-*-*t, M4-lt>)M)
HONS 220841
AFOIlTiS"
U9t 4. SUMMARY OF TETfiACMLOftOPHENA2INES DETECTED IN OFF-GAS Samples !
SAMPLE t.O.
hCi Gas washing Bottle 41 MCI Trao Solution NaOn Gat washing Bottle 101 Na> Iran Solution Teflon Tut>e Connector Batch a Scrapings
TOTAL TETWCML0e0PMN*2iNE (uq)
4 7.2B k 10
4 3.99 k 10
11.2
IB.O
I.3S
414
TOTAL
4 11.31 x 10 ug
* 113 mg
HONS 220842