DIMETHYLNITROSAMINE IN THE BALTIMORE
   AND BELLE, WEST VIRGINIA ENVIRONMENTS
     DR. EUGENE SAWICKI, ACTING CHIEF
   SAMPLING AND ANALYSIS METHODS BRANCH
ATMOSPHERIC CHEMISTRY AND PHYSICS DIVISION

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                              AGENDA



Title:  Dimethylnitrosamine in the Baltimore and Belle,  West Virginia
        Environments.

Place:  Auditorium, ERC,  Research Triangle Park, North Carolina 27711

Date:   January 6, 1976

Time:   9:15 A.M.
9:15 A.M.                         Opennng Remarks
                                    Dr.  A.  P.  Altshuller (EPA)

9:30 A.M. - 9:45 A.M.              Formation and distraction of  N-N
                                  dimethylnitrosamine in ambient air
                                    Dr.  Phillio Hanst (EPA)

10:00 A.M. - 11:00 A.M.           TEfi Analysis of dimethylnitrosamine
                                  found  in the Baltimore and Belle,
                                  West Virginia environments
                                    Dr.  David  Fine (Thermo Electron Core.)

11:15 A.M. - 12:15 R.M.           G.C./M.S. Analysis of dimethylnitrosamine
                                  and other pertinent organic pollutants
                                  found  in the Baltimore and Belle, West
                                  Virginia environments.
                                    Dr.  Edo Pellizari (RTI)

1:15 P.M.  - 1:45 P.M.            Analytical  findings of FMC Corp. for
                                  dimethylnitrosamine at plant  site operations
                                  in Baltimore, Maryland

1:45 P.M.  - 2:15 P.M.            The analytical findings of DuPont Copp.  for
                                  amines and dimethylnitrosamine at plant site
                                  operations in Belle, West Virginia

2:15 P.M.  - 2:30 P.M.            Break

2:30 P.M.                         Discussion and Closing Remarks

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  Atmospheric Chemistry of N-Nitror.o Dimethylamine
         This ia n prel Lriinary report that
         has not yet been reviewed or approved
         for publication.
                        by
Philip L. Hanstf John W. Spence, and Matthew Miller
      Environmental Sciences Research Laboratory
             Environmental Protection Agency
    Research Triangle Pa;rk, North Carolji:a 27711
                 January 5, 1976

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Summary

     Gaseous dimethylamine, (CII_)_ Nil, has been shown to react with

gaseous nitrous acid, HONO, in air to yield N-Nitroso dimethylamina,

(CH ) N-NO.  The N-Witroso dimethylamine decomposed  in sxmlight with a

half -life of about 30 minutes.  Long path infrared absorption spect-roscopy

was used to monitor these reactions at conrentration levels of parts-per-

million.  From the reaction rate measured with HONO, it is estimated that

some nighttime nitrosation of dimethylamine might take place in a heavily

polluted urban atmosphere.  Such nitrosation reactionr. would diminish

rapidly after sunrise, and accumulated nitrosamine would be decomposed

by the sunlight.  Any N-NitroGO dimethy3amine detected in the oir in the

afternoon would have: to be the result of direct emissions rather Ih&n

emissions of precursors.


Introduction

     Two questions to be answered about nitrosamines sue  (1) will they

form in the ambient air, and  (2) how long will they  last in the preoc-nce

of sunlight.

     It has been known for many years that ammonia and amines react vith

nitrous acid.  The reactions are set forth in the organic chemistry text

of Lucas as follows:

     Ammonia yields molecular nitrogen and water:
                        .
            N-i'H   "  " ""••'/   •*•   N===N  + 2H 0
              SH   .  .   of                   2
     Monomcthyl aminc yields molecular nitrogen, methyl  alcohol,  and

     water :

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Summary



     Gaseous dimethylaminc,  (CH ) _ Nil, has been shown to react with
                               •   N=N  + 2H 0


              *VA     .   °i

     Monomethyl aminc yields molecular nitrogen, methyl alcohol,  and



     water:




                                    —1—

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                     tu
             CH   -  Ml     0 « H-OH  ->•  N^N + C1I OH  + HO
               J     I i"l    I                      «3       &
      Dimethyl C:N:SO  yields 11-Nitro- o dimothy] aipine  and
             CH
                     . ---------              3\
                   N -A II     HOI- 13- O  ->-      ^N-N=O 4  HO
                      L ----------              '
      It is also  known that r.itroso  c:o:n]jounds are  light sensitive.

 Th<.:y absorb o] {.Eiiviolet r^dxaLton r,:ir> iivy diorociatt o:: i^.oi.ierj xe .

 It. is worth noting that many past yec;r& of study  of the photochemistry

 of atmospheric oryanic compounds and nitrogen oxides have not shown

 nitroso compounds  to be reaction products.  It.  is therefore necessary

 to cst.'iblinh  the bchcvior of N-Ilitii-^o d inethluinj no ui'dec ficLuaJ L;un-

 ILyht
      Measurements  wcro made of the  rote of format, ion o." II-lli

 dimethylamine  from dimethylamine  and nitrous acid  in air.  The nitro-

 £i-'i'_io:i \.'c;:; corri .d ouL in c. cylJnrfncnl glans rc-,;cl:ic:i clsrnibr-r 9 mrttci.s

 ](.^iy ar.c! 0.3 iti^l.c-v." in f3.i j;'iCil-or.  TliC reaction  chaii-jjcr is LurTOunOc.ci jy

 9G f luovcsceijt lr»mps to allow study of the photochemica]  behavior  of

 1.3." rec-.ctdriLs  c,ocl  producuy.  The-;  chc-v.'.jer conL&Dns  a n.uli.iple-pass.

 mirror system  to allow in situ analysis of reactants and products  by

 infrared absorption spectroscopy.   The absorption  path length was  350

•meters, allowinq monitoring of gases au concentration!; do-.-n to 0.3  pp.rt-

 po1:-- iil] ion  (PJ^f }  In ciir.  Spectra  \:^j:e rp-ccrded by r. four lor Ti any form

 Spectrometer.   Tha syr-te;i' is diaqL-j'Ti^d in rigui'u  1.

      Dimethylaminc liquid was purchased from fisher Chemif al Company.

 N-!Iitror:o dimethyl dminc was prepared by mixing  in  a gla-js vessel 20

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Torr. of  dimethylamine vapor and 20  Torr.  of nitric oxide, and then


'fiduv'-.tting room air until the total pressure reached one atmosphere.


A mist  of products formed.  Volatile components wore pumped out of


the vessel,  leading liquid nitrosamine.   The nitrosamine was then


vaporized into tha reaction chamber.   Figure 2 shows the: spectrum of


approximately 10 Torr. of dimethylamine  in a 10 centimeter absorption


cell.   This  is equivalent to 3.7 ppm in  the 360 mater cell.  Figure


3, upper  portion, shows the npictrum of  H-Nitrosio dimethyl anu.ne &\'. a


concentration of between one and three PPM in the 360 meter cell.  The


spectrum  in  the upper portion of Figure  3 is similar to the spectrum


of liquid N-Nitroso dimethyl amine reported in the Aldrich Library of

                  (0)
Inijr-'ired  Gpec:i:ir.-\.


     The  photolysis of H-K:i. tror-;o c!.uno.ti.'yl£min« w .:"=•. stv-^ied I^oth in


the lt.boriito::y reaction c]ia-:i]->ci: arn'l  in ;: 2'j cubic foot Ted] ta bsg


exposed to real s\:.ilight.



RSultS
       itroEicitir." experiments v;ere  c^rricfd out witii a dry NO--KO   rr:'!.>;ture


in nitroge:i,  r-.;j well as v.'.ith a nitroxi^  
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      When 1 ppm dimtithylamine was mixed with 0.5 ppm nitrous  acid




vapor in equilibrium with about 2 ppm 110,  2  ppm NO , and  13,000 ppm




II  0  in ruo-m air, ('.'•'.'. i;iuiri<.; v.'.v:.-.: j:r;:c ;.•«.;•;; at  ;-A  rate of about 4 porccf.at




.per  minute.  Fitjurn 4  shows infrared absorption spectra of a  renctnnt.




mixture, rt the bo;rj:i nniny of the reaction and 45 minutes later.   Thi;




spectrum at the start  shoves bands due to dimethylamine, nitrous acid,




and  some aRMtionia iivip.urj.ty.  The spectrum after reaction shows dimethylamine




nearly completely reacted wh:;.le the nitrour.  acid, and' anurionia  are slightly




reduce-:--"1' froui the:!.:•: starting amounts.  This spectrum also  shows a new




band at 1020 cm   due  to the N-Nitroso dimethylamine.




      For the photolysis experiments in the laboratory, the nitrosamine




was  rri.iv.cd v.v'.th ;;.'•.r :in  the. reaction ce.'i 1 and  irradiated v;ith the bank




of u.M:.j:;i'.':i C'.'i t:t '.''.; M-.^I :: fc-:: p^rioc'" up to one hour.  Fiqors  3 sho'.-.'t; the:




spi.:.'i.'Lvuin bciforo .••.;•''! ;: ,''to..; .i.rrarli.r.i'.ic::1;.  Mote th?t in '.;;•'•?  hour- \'.hz -r.:'.i.ro-'




snmine was ncaxO.y -'.'ulJ.y convertod to a new compound l:h.-;t  has  a distinctly




different set of absorption bands.  This new compound has not been identified




but  some information has been derived from the spectrum.   There is no OH




stvctchiuvj c'-.bsor:.v:--;.oi'i  b'ina in vlic spcccrum,  and the CU stretchino fre-




quency in the new r..pectrum is considerably wealcer than in the spectrum of




the  original M-K::.i..j;oso ciimel'-hylaminc--..  Other photolysis products seen




when the spectrum is recorded at higher resolution include nitric oxide,




carbon monoxide, and. formaldehyde.




      The samples photolyzed in the large Tedlar bag were  analyzed in the




infrared absorption cell before, and after  th-sir nxposure  to sunlight.




An inert trace): confound, Freon 11, was added to the sample to j.ndd c;ite




any  dilution or loss of sample, in handling.   The nitrosamine  concentrations
                                     -4-

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before and after irradiation were determined as ratios to the  Frcon 11



concentration.';.   Tho.v.e sunlight j'-hot o.lyr;u.': wort' carr.i.ed out on two



different days.   On a cloudy d.-iy between  11:00 a.m. and 12:00  noon,



half the N-Nitroso dimsthylanune. V.YJ.S destroyed in one hour.  On a



clear sunny day  between 11:00 a.m. and  11:30 a.m., half.the N-Nitroso



dimethylamincj  V.'C.K destroyed iii c-ie-lio.lf hour.
     The experiments have shown that  in  drv  ?..ir,  NO gas and NO,  gas do not



react with  dimethylamine vapor at a rate that could be appreciable in



the atmosphere.   VJhen water vapor is  present in the air, however,  the



formation of  N-Nitrc.so diiiiethys.'l.ivdne  doss; proceed at a significant



rate.  This ro::u.V,; ir.c-fi: clearly- ir. duo to the ga.i1-•-_:.:•}-.r-so ^ormv.-ri'rn  of



ri.ttroiu; ricid.




                   NO -I- NO  + H 0   -v  2  HMO




This equilibrium has been well documented.   Recently, Calvert,  et.al.,



have given  the  following value for the equilibrium constant at  ?.3  degrees



Centigrade.





                   K    =         2           ~- 1.5 x 10~& PPM"1
                    eq.   	

                       i    p  . p     • p
                            NO   WO     HO
                                   ^      £•
From tliis  constant,  tho waounts of nitrous acid reacting with  cli
wore calculated.   RMGY.'lcd.oa of the HKO- concentration, the d.v.uethyla.r-une



concentration,  ar.d the rate of disc^.ppearancc of dime thy lanu:ie,  combined



with an assumption of a bimo.Ic?cular  re.aci:ion:



                   (CH3)  1-3 H + HOKO .-v   (Ci!^) .  W=KO + H, O



allov/s a  rate  constant to be calculated for the expression:




                                   — 5 —

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                          1 L«I   _    .

                         .                (CH) NH    HOMO
                        at                  3 2




The value  obtained is k - 0.00 ppm "  Mir;.   "  From this constant, an



upper limit  can be calculated for  the  rate of N-Nitroso dimethylamine



formation  uynfe- any a:;r^;Kr:i.   \?hc.r! the sun j:i:ies,



tl?e nitrous  f?.c:L("' ^s clrptroyed by r-hotolysi^ r-.u.-: ;; 'r.-..:.-;x ::• i:;>"u»"it" 'i.:;.;\ }5>.-'~



reformed by  the relatively slow  termolecu]ar reaction c.il MO, MO , and



^0.  Nitrosation therefore cannot take place in the  daylight.



     The scMvs  light that rtops t)ip. nitrosction process v;ill destroy the



accuwu.Tatc-.1.  i:3-H.ir.roso diif.^,ti)ylo:rii;-.c;.   J'.s r::p^i:ti.:d above, at l:u.ll Kur.'] ight



half the nitrosamine will be  destroyed in half ;:.n hour.  Between 0:00



a.m. and Noon, any M-Nitroso  dimethyl&Tyd.n:; £icc\v.,-u.'!ated during tho night



would be reduced to less than one-half of one percent of its starting



concentration.  After ten hours  of daylight, only one molecule in one



million will remain.



     The r.t.udy of photolysis  products  is not complete.   To date,  thrc



results have shovn that the destroyed  W-Mitv.o.so di;:ic!.hy.lamine is re--



placed by  a  mixture of nitric oxide,  carbon monoxide,  formaldehyde and



an unidentified 'compound v.'hose spectrum is • shown in Figure 3.  A





                                    -6-

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weakening  of the c-H band  indicated that th.is  lal-.t.e.t compound may  only



contain  a  umall f. rant'. ion of  tho stnriring material.   The spectrum of



products does not exhibit  any O--H stretching frequency, thus indicating



that a molecular rearrangement to an oxime doe-.-,  not tako place.  In



this respect the gas phase photolysis differs  irorn the liquid phase


                                        (4)
photolysis reported, by yuan-Lang Chow.



    . The largo vitric: oxide  yield indicates t.h;.:t the photolysis  breaks



the 1J-H  bond:



                        N-MO  + hv  -*•
The radical  (CH )  H most  likely gives up methyl  radicals that are  further



oxidised  to  the CO and H  CO  sncn as products.  It FCO.IT.S possible  that the.



vm rlo1 ••:.•• 1 1. i. . /!      .>        .->  .


study.




Conclusions



(1)   It seems reasonable  to  conclude that atmospheric formation of N-



K:it::oso d.imethy.'if.nJ.r^i should no! b'2 rct/rrded c.z  a coviou.': . gene.r-i'l  prcbilem.



Thi.s  conclusion . is bc-;sed  on  tv.-o factors.  First, the reaction between



diricthylfJiiine arid nitrous c\c.id. vjj.ll only occur to .un sppreciab!! a  exvont



while the  amine is confined  to a region of heavy urban air pollution.



The second factor to be considered is that dimethylamine is not a  gen-



erally distributed air pollutant;  the problem  vill arise only in  the



vicinity  of  m.ri,m:factux'ing plants that release  the an.inc.



(2)   The  indic.-.i.cd jion-form-^.trLon of the nitror;amine during tlifi  daylight:



hours requires that any nitror.am.ine detected in  the air in the  afternoon



must  have  boon emitted as nitror.amine rather than in the form of pro-



cursors.



                                      -7-

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(3)  The  deKt.rucV.ion  of H-Nitroso <3imethy.lami.nu by sunliyht will prevent

day-to-day act:u'Tiu.lat:;.on o>' the  coMpov.r.ci :i.n  t/v/  nvr.  Tt  seems reasopc-.bl e

to assume that any • N-Nitroso dimethylamine  that may be present in par-

ticles  in the?, nir wil.l also be;  oer-ioroycd by photolysis.

(4)  Formation of H-Nitrof>o dimtithylamine would take place more readily

in industrial c* t. or o. sphere. 3 than  in thr: ambiept  air, because indoor il!u-'.hci:o."lvtic  'l.rs-

truction  of ej.ther  the nit/:ous  ?.ciC. /:eactci?it or the nitrosaruine product.
1.  Organic Chemistry,  Howard J.  Lucas, American Book Company, New  York,
    1935.
?.  Cpsctro-^copic Studies of Pho;.o"!'i :-..•! c;J.  Sivioc; :•••!. •',..-. .r  .'.';-.? .'.-I ,'iV
    Detection, .'J.G.  Cnlvort, W.H.  Cli.-..n , R.J.  J]o;j' ..;:::o....  uci .'; .  jj. ^
    Ohio State University, 1975.

4.  Yuan-Lang Chow,  Tetrahedron  Letters, 33-34, 2333,  1964.
                                       -8-

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-------
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    N-NITROSAMINES IN URBAN CQMMUNnY AIR
               PROGRESS REPORT
         EPA Contract 68 - 02 - 23121*1
                 Submitted by

         Thermo Electron Corporation
      85 First Avenue, Waltham, MA  02154
                 Submitted to

        Environmental Protection Agency
Research Triangle Park, North Carolina  27711
    David H. Fine (Principal Investigator)
               January 5, 1975

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1.  INTRODUCTION
     In September 1975* Pine et'al reported on the presence of
di!r£thylnitrosamine (DMN) in the air in Baltimore, and Belle,
West Virginia.  The work described in this progress report re-
lates to a brief but intensive effort to obtain additional in-
foraation on the possible presence of nitrosamines in air in the
vicinity of a primary source in Baltimore, Maryland and of a
precursor source in Belle, West Virginia.  Air and water samples
were collected on three field traps:  the first to Baltimore
from October 15 through October 22, the second to Baltimore and
Belle from November 19 through December 5, and the third to
Baltimore from December 11 through December 16.  In order to
greatly expand the data gathering capability for the second and
third field trips, the specialized TEA Instrumentation was mounted
inside a mobile laboratory.
2." VALIDATION OF ANALYTICAL PROCEDURES
     A series of experiments were carried out so as to ensure
that the new TEA analytical technique for nitrosamines was in-
deed valid.  Of particular Importance was the concern that the
observed DMN levels may have been due to an artifact of the
collection and/or concentration technique itself.  These defini-
tive experiments included:
     1.  Parallel analyses using two different techniques.  Thermo
         Electron collected air samples cryogenically, and analyzed
         them on their TEA instrument.  Another independent EPA
         contractor, Research Triangle Institute, collected their
         air samples on a Tenax gc cartridge, and then analyzed
         them by means of gas chromatography - mass spectrometry.
         Both contractors confirmed the presence of DMN, with
         the quantitative agreement between the two sets of data
         being within the limits of experimental error.
                              -1-

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     2.  With the TEA Instrument mounted Inside a mobile labora-
         tory, air samples were  analysed directly, without  any
         solvent extraction,  or  concentration whatsoever.   Direct
         TEA analysis confirmed  the presence of EMM.

     3-  The precursor amlne, dimethylamine, was added to each
         cold trap.  Conversion  of the amine to the  nitrosamine
         was not observed, even  when 100,000 times excess amlne
         was added.  The tests were carried out both in the
         laboratory, and in the  field on the FTC property.

     4.  Excess nitrite was added to each cold trap.   On no
         occasion did the added  nitrite give rise to an increased
         DMN level.  The tests were carried out both in the field,
         and on the FMC property.

     5.  Even in the presence of large ambient air levels of
         dimethylamine, only  trace levels of DMN were detected.
         This test was carried out on the Dupont property.


3.  BALTIMORE

3.1  flATA ON FMC PROPERTY

     Twenty seven air samples were collected on the  FMC site,

with many of the samples being collected close to the unsymmetrical

dimethylhydrazlne (UDMH) plant itself.  The observed DMN levels
                    •3           O
ranged from 1.9 pg/m  to 36 yg/m .  The levels found varied con-

siderably.  Four samples taken on October 15, 1975 at the East

parking lot contained 13, 15, 11 and 8.6 yg/ra.  On  November 19,

1975 DMN levels close to the  UDMH plant were 36, 11, 7.6, 15, 15,

30, 8.9 and 10 yg/m3.  On November 24, DMN levels of 2.8, 2.0,

4.5, and 5.5 were found.  Two of the stacks were also monitored,
                                        o
and were found to contain 12  and 14 yg/m , respectively.

     A rain water puddle close to the UDMH plant contained over

6,000 pg/1 (ppb) of DMN.  A mud  sample in the same area contained

over 200 pg/1.  A water sample from a drainage ditch on the border

of the FMC property with B.P. contained 5.9 yg/m3.  Water taken

directly from the adjacent cove, contained DMN levels in the 0.26

to 0.94 ug/1 level.

                              -2-

-------
3.2  CQ'MENTY AIR DATA WITHIN ONE MILE OF FMC
     Thirty air sarples were collected, with observed DMN values
                       o            o
beirg in the 0.002 vg/iir to 3.0 yg/nr range.  The average DMN
value found was 0.5 ug/m .
3.3  AgNDEL COUNTY AIO DOWNTOWN BALTIMORE
     Sixteen samples v;ere collected In regions far removed from
the ?!'£ site.  DMN levels ranged from 0.026 ug/m3 up to 0.125
yg/rr.  The data in Arundel county show a decreasing DMN level
In the early hours of the morning, starting with 0.11 vg/nr at
3:^5 a.E. to 0.036, 0.031, 0.023, 0.021 and 0.016 at 12:35 p.m.
However, in downtown Baltimore, the DMN levels increased from
0.025 vg/ta3 at 6:42-7:55 a.m., to 0.088 ug/ta3 at 8:25-9:25 a.m.
and 0.11 ug/ia3 at 9:25-10:25 a.m.  The fact that significant
EMS levels were found so far from the primary DMN source suggests
that there are other sources of DMN in the area.
3.4  vansa DATA FRCM STONEHDUSE COVE
     Water samples were collected by Thermo Electron and also by
EPA personnel.  Storehouse cove was shown to contain DMN, with
levels ranging frcn about 0.09 up to 0.94 yg/1 (ppb).  Even 1
mile free the FMC site DMN was found at the 0.09 ug/1 level.
Three sets of samples were taken at the surface, and at depths
rangirjS from 6' to 20'.  In all cases the DMN level at the sur-
face was less than the DMN level below the surface (0.035-0.14;
O.CC5-0.14; 0.056-G.13, respectively). A water sample taken from
a se-,-;age treatment facility adjacent to the W£ site contained
2.7 ys/l of DMN.
                               -3-

-------
4.  WEST VIRGINIA
     In Belle, as In Baltimore, the earlier findings of Fine et al
were confirmed.   Observed DMN levels ranged from trace levels
to 0.73 yg/m  - the latter sample being taken at the Dupont
facility main gate during a temporary weather inversion and was
the highest value which was found in the region.
     Several tests were carried out at Dupont, and also at Union
Carbide.  The levels found at Union Carbide were low, namely
0.030, 0.022 and 0.016.  At Dupont, DMN levels up to 0.46 yg/nr
were found nearby their amine area.
     Waste water samples taken from Dupont showed the presence
of DMN, at levels of 4.2 2.3, and 2.4 ygA.  A waste water sample
from Pike Chemical Company in Nitro, also contained DMN; at the
3.0 yg/1 level.  It is suspected the the DMN levels in the waste
water arise from either DMN Impurities in the amlne process, or
subsequent nitrosation of the amine in the waste treatment facility.
5.  NEW YORK CITY
     In New York City, an air sample taken on 'the road, 2 miles
east of the George Washington Parkway was shown to contain DMN
at a concentration greater than 0.80 yg/m .
6.  CONCLUSIONS-
     1.  The earlier Pine et al report on" the'presence of DMN
         in the urban community air of Baltimore and Belle has
         been confirmed.  Higher levels; were found than those
         first reported.
     2.  DMN levels on the PMC site in Baltimore were up to
         thirty times greater than first reported.
     3.  There is every reason to believe that the UDMH plant is
         the major source of airborne DMN levels on and Immediately
         adjacent to the PMC property.
                               -4-

-------
4.  There are other sources of DMN In Baltimore,
    possibly a nearby sewage treatment facility.

5.  DMN has been found in waste treatment  water, both in
    Belle and also in Baltimore.   This is  the first report
    of the presence of DMN in water.

6.  DMN is a much more widespread pollutant than was origin-
    ally anticipated.  It has been detected In the air at
    most of the sites which have been examined so far, namely
    Baltimore, Belle-West Virginia,  and New York City.
                        -5-

-------
                                                        COMMUNITY AIR RATAi
                                  PROXIMITY (LESS THAN ONE M1LEI  TO F'MC PROPFRTY.  DAI TIMORf
                                                                 1975
Lab
No




60
61
n?
70
71
i
J
K.
L
T
L>
AA
I»D
13Z
133
134
135
136
ISO
1S1
152
153

63
64
65
PJate
8-22
8-22
8-;:
8-22
lO-lo
10-lu
10- '»
10-22
10-22
11-20
M-20
11-20
11-20
1 1-22
11-22
11-25
11-25
12-11
12-11
12-11
12-11
12-11
12-15
12-15
12-15
12-15
8-Z3
10-17
10-17
10-17
Location
F rankfurt Avenue
Frankfurt Atomic
Northhridpe Avenue
Northbridge Avi-nuu
Patapsco Sew .T Re Plant
Patapsco Si-wage Plant
1J I'iio^co Srwape Plant
Norlhbndgi- Rd
Northhrtclge Rd.
Conoco. Corner Fairfield and Chesapeake
Conoco. Coiner F'airfield and Chesapeake
Minerac Curp
Ml m-rac Corp.
200 Yard's. l~n«t F MC in B Plot
200 \ards. E.nt F MC in D Plot
Noilhhndpe and Canm>rv Road
\orthbridpe and Cannery Road
Camer\. 4th (Plavground)
Corner Canierv and 4th (Playground)
Corner Cannery a -id 4th (Pla\ ground)
Corner Cannery and 4th (Playground)
Corner Cannerv and 4th (Plavgrnundt
Corner C.inncrv and 4th (Playground)
4th St ind Highland Ave . 4 Corners Restaurant
4th St and Highland Ave
4th St. and Canntr) (Plavground)
Chc-ssv Coal Piers
Chessv Coal Pier*
Che-"-\ Coal Pu-ri
Clu »»» Coil I'-i-rs
tt rather
\\ md




N. NW. 9 Knots
N\V, 10 Knots
NW. 9 Knots


SU. 6 Knsts
SU. 3 Knsts
S, 4 Knots
S, 4 Knots
W NW. 7 Knots
U NW. 7 Knots
WNW. I ight
W Ntt . Light





E, Light
S\\
sw


E, NE. 7 Knots
NNF. 7 Knats
F-, 14 Knats
Te-np




72
73
72


70
61
57
*7
^9
47







Cold




56
5n
56
Muc









Clear
Clea r,
Cloudy




Cloud\
Overcast
Clear.
Sunnv
Clord\
Cloudv
Cloud\
Cloudv
Cleir
Cl.nr
7 16 mm llg



Htm
Katn
Time
i-ll am
1 -3 nm
7." nm
! - 3 i>m
II 10-1 10 pm
1 30-3 30 pm
3 50- * 10 nm
4 10-5 10 pm
8 30-o jn pm
3 45-4 iS im
5 00-6 00 om
8 20-o 20 pr-T
o 30-10 20 n-n
115-215 om
2 15-3 15 om
12 3S-I 3K.ni
5 OO-o CO um
1045-11 45 ai-i
11 58- i: 5t- ont
1 45-.' 45 p'li
2 51-3 M nm
4 00-4 10 Till
7 37-8 17 .im
12 40-1 4flpm
2 32-4 32 pm
6 5S-7 30 pm
7 00-9 00 pm
II 00-1 00 nm
1 15-3 15 pm
3 45-5 45 pm
mix
MU'rn
\!J
\l)
0 10
0 06
\r>
\')
Ml
1 4
0 41
0 3J
1 8
0 17
n 33
1 t
3 0
n \f
0 76
0 212
0 OoO
0 
-------
                                                      AIR  DATA FMC PROPERTY. BALTIMORE (1975)
Lab.
NP
A
3
C
D
E
F
G
H;
H2
M
N
O
P
\ 1
\1
W 1
W2
X
sr
sr
^
Zl
Z2
So
57
5H
59
Onte
75
1 l.|0
1 ! - 1 °
1 l.|0
1 l.|0
1 l.io
ll.io
; i-io
H.IQ
1 l.|0
• 1.21
1 1.21
11-21
1 1.21
1 1.2-1
1 1-24
11.24
1 '.24
1 1.24
11.24
1 1.24
1 '.-"
'M-N,
I.J**--
10-15
lO.'l
10-15
10-15
Location
N\l ot thermal destructor
NW of thermal destructor
NW of thermal destructor
Next to ammomn plant
Next to ammonia plant
Next to ammonia plant
Next to ammonia plant
Next to ammonia plant
N>.\t to .ii-.imoma plant
1 5 ft S of ammonia tanks
15 ft S of ammonia tanks
15 ft S of ammonia tanks
1 5 ft S of ammonia tanks
S ol *>£ cnr of dlrnuiine plant
S of SE cnr of dimuzinu plant
5 of SE cnr of dimurinu plant
S of S£ cnr of dimurmc plant
S of SE cnr of dimuz.ni: plant
Therir.il destructor stuck
V602 wet scrubber
S of SE ..nr of dimuzinc plant
S of SE err of dimuzinc plant
S o' ."iE i.nr of cl.m^ziic plant
E parking lot
E parking lot
E parking lot
E park.ng lot
Weather
Mina
E. 3 knots
E, 3 knots
N. 5 knots
S. bW, 2
S. SW. 2
SW. 3 knots
SW . W. 3
Calm
Calm
N. 5 knots
N. 5 knots
N. NW. 3
N. \'W, 3
NE
NE
NE
NE
NE
NE
NE
NE
NE
NE
\V, SW. 10
SM, 10 knots
SW. 9 krots
bW. 5 knots
Temp
65
65
65
61
60
5". 5
60.0
52.0
52 0
57
57
51
51










87
86
85
80
Miic.


Clear








Rain
R.Tin














Time
1 -50-2 50 om
3 00-4-00 pm
4 05.4.25 pm
5 30.6-10 pm
6 40.7:40 pm
7 40.8 40 om
8 40.0 40 pm
9 45- 10 4S pm
9-45-IO'45 pm
2-15-3 15 pm
2 15-3:15 pm
3 20.4 20 pm
3 20.4 20 pm
1 1 40.12 40 pm
1 1 40-12.20 Dm
1 00.2 00 pm
1 00-2 00 pn
2 55-3 55 nm
4 25-5:00 prr
5-05.5:50 pm
7 00-8 00 pm
7 00.8 00 pm
7 00. S 00 pm
12-17. • J5 om
2 30-3 30 pm
4 i5-5 4S o-n
6-00.7 00 pm
DMN
; C
/•g/m
36
i 1
7.6
15
15
30
8 «
1 1
0
16
12
3.3
3.1
2.8
3.2
2. i
1 •>
4.5
i2
14
5.5
5 6
5 1
n
15
II
8 7
Comments







.split sample •* normal
' •* nitrosated
>-» rtt-nethylamlnc added
'•» normal
>•* dunethylamina added
' •> normal
l-» normal
-* mtros.ited
i Jh dimuth^lamine added
' -!• ior-n.il

S'ack sample
Stack sample

I •* normal
' -> pi'-osnted




NO NO,
ppb

















8. 60
7. 05
5. 70
13. 70
TKERMO ELECTRON RESEARCH CENTER
WALFHAM,  MASS.  0?I54

-------
                                                 COMMUNITY AIR DATA
                                           BALTIMORE AND AR'JNDEL COUNTY
                                                           1975
Lab.
No.
Q
R
S
145
146
147
148
149
137
138
139
UO
141
142
143
144
Date
11-2Z
li-22
11-22
12-14
12-14
12-14
12-14
12-14
12-13
12-13
12-13
12-13
12-13
12-13
12-13
i2-13
Location
Corner Howard and Preston
Corner Pratt and Commerce St.
Corner Pratt and Commerce St.
Corner North Baltimore and We*t
Liberty on West Fairmount Avc.
Corner Lombard and Cnlvert Ave.
across News American Building
Libertv and West Fayette St.
South Street and Pratt Street
South Street and Pratt Street
Cov Ritcnie Highway, Bres'-Uyn
park Pla/a Shopoing Center
Rt. 2. Gov Ritchie Highway
Stahl and Ordnance Rd.
Solly School, off Fort Smallwood
Rd.
Park. West Day Ave
4th and Edison Street
Spruce and Fairhaven Avenue
Spruce and Fairhaven Avenue
City
Baltimore
Baltimore
Baltimore
Baltimore
Baltimore
Baltimore
Bait-more
Baltimore
Aru.idel County
Arundel County
Arundel County
Arundel County
Arundel County
Arundel Ccunty
Arundel/
Baltimore
Arundel/
Baltimore
\\'eather
Wind
Variable, 2 Knots
'A', SW.7 Knots
W,SWr,7 Knots
W, SW,7 Knots

SE, 5-6 Knots
S, S\V,6 Knots
S, SW, 6 Knots

E, NE
NW

N, NF. 10 Knots



Temp.
41
47
47

41'F
42
42
42

44'F
45'F
44'F
44 "F
44
44

Misc.
Clear
Cleir
Clear
Fogey
Fog
Fog Lifting
Overcast
Cloudy
Cloudy
Light Rain
Light Rain
Overcast
Overcast
Clovidy
Cloudy
Cloudy
Time
6 42-7 55 am
8 25-9 25 am
o 25-10 25 am
6 35-7 05 am
fi 00-9 00 am
° 00-10 00 ?m
10 50-11 35 am
11-00-11 45 am
3 45-4 54 am
5-55-7-13 am
7 29-S-29 am
8 53-9 42 am
10 05-10-50 am
1 1 02-12 35 pm
2 00-2 45 pm
3 00-3 45 om
DMN
uR/m
0 026
0 088
0.11
0.04°
0 048
0 022
0 028

0 111
0 036
0 031
0.023
0 02!
0 016
0 125
0.116
THERMO ELECTRON RESEARCH CENTER
WALTKAM.  MASS.  02154

-------
                                                    '  COMMUNITY AIU DVI A
                                                 WEST VIRGINIA (CHARLESTON, BELLE)
                                                               1975
Lab
No.
1
2
3
4
5
I *
-
8
0
10
i:
\z
13
U
16
17
ia
19
20
21

Date
11-30
12.1
12-1
12-2
12-2
12-2
12-2
12-3
12-3
12-3
12-3
!2-4
12-4
12-4
12-4
12-5
12-5
12-5
12-5
12-5

Location
Holiday Inn No. 1 • '•
Dupont, West End Parking Lot
fXoont, M.I in Gate Near Offices
Dupont. \\ i-*t Und Parking Lot J
Residential, Corner Ciliforma '
and Washington Street • ' ,
a'-ooncys Big Bov S:aH
Dupnr.t, Amint: Arra <
Union Carbide, Blames Island
L'r.ion Ca-buic, ni.iincj Island
Union C.-.rhic!e, VmtoisLot
15th Slrci". rfnri KIMTV rw D-ivc
No. 8 p imp Pit, East Side Over
Flume • • r
Above No. 3 Aerator, Mixing Tank
Mixer Sox for Sludge . ' I !
Clements Resi.'ii'-ant ' ! ,
An-i-.e Production AreJ
Main Gate
Main Gate
Betty's Pir«i, Near Town Office
Fike Chemical

Town •
Charleston
Belle
nelli
llullc
Charleston
Kanavi'na
r>v ile
South Charleston
South Charleston
S^uth Chir'.cston
iln.ionl Town
Dr.pT 1, Belie
Dupont, Drlle
I3uoo.it, Belie
CHjrlestnn
Duoon*. Ui'"c
O^pont, Dclle
Dupant, 13 r Ik
B-:'..;
N : .-.

U ind
SW
Lipht, Variable
Liclit, Vari.ibl.-
SI , •) Knoti
W, 5 Knots •
S, SV. , 3 :- ',
• 43' :
h ( Dupor '

-
•




.

•

—

Invrsion



THERMO ELECTRON RESEARCH CENTER
WAL.THAM, MASS.  02154

-------
                                          WATER OAT A.
                                    SUMMARY OF PMN LEVELS
                                               1975-
Lib
No.


 "2", 20"
Stonchouae Covt>, Buoy S *4", Sur.
Stonehouse Cove, Ruov S '4", 20'
Stnnchouse Cove, Buo> N "6*, Sur.
Stonehouse Co/c-. Ij'iuy N '&', 6'
5th and Riverview Drive Pier, Kcinavka
River
WTP Effluent i '
V. nstc Treatment, Mix Tank
No. B Puinphcail, Waste ^.itci
From CST, Corp. Sew Treat.
Notea
,
i : :
Sec Map
See Map
Srr Mip
See Map
See Map ,
See M.ip

FMC :'.*p
FMC Map
TMC Mip
1 MC Map
FMC Map
FMC Map
FMC Map
i i
Collectrrl by Er'A
Collor.trd by EPA
Colluded by EPA
Collcctrd by EPA
Collectrd by EPA
Collected by EPA

Dupont
Dupont
Mo. 1 S35 .Dupont
Fike
Town
Waltliam
Boston
Ualt Iniore
))al:imorr
Baltimore
Baltimore
P.altin-xire
Halt i more
Bnliimpri
B;ilf .mo.c
Bali 1 ..or?
Hr. U ii.ii) r
Ua It lino i r
DaUinioi i
Baltimore
Baltimore
Baltimore
13 ill imp IP
B; !( invre
B.ullniorc
Balliir.'irc
Baltimore
Belle
i i
Belle
Belle
b.'lie
Nitro
DMN
MB'I (ppb)
N. D (<0 01')
N. D. (
-------
 PATAPSCO  RIVER
     HARBOR TUNNEL
      N

      S
  SOUTH
BALTIMORE

-------
       DMN CONTENT OF WATER SAMPLES
                                                     SHIPLEY
                                                    TRANSFER
                                                       INC.
                                                    AMERICAN
                                                    ALCOLAC
                                                  CORPORATION
                                       MINEREC
                                     CORPORATION
CONTRACTOR  I
PARKING LOT

-------

    J_
0246
  TIIWIF I MIM \
                          AIR SAMPLE
                  TEST OF DIRECT SAMPLING  DEVICE
                LOCATION: NEW YORK CITY 2 MILES EAST OF
                         GEORGE  WASHINGTON BRIDGE
                   DATE: NOV. 17, 1975
                   TIME-' n^-GRM.
                SAMPLE TIME 3 MIN
               SAMPLE VOLUME 3L
                 RESULTS:
                        @ DMN-0.82jirj/nf

-------
      A.
A
        I
                  rr
B.
       4       02
        TIME (MIN)
    6
           AIR SAMPLE

  TEST OF DIRECT SAMPLING
           DEVICE
LOCATION: FMC DIMAZINE PLANT
                                     DATE: NOV. IS, IU7

                                     TIME: 10:30 A.M.

                                SAMPLE TIl'E 3 MIN

                                SAMPLE VOLUME 31.
                                  RESULTS:
                                          A. DMN-UNDETECTABLE
                                                 ) 01- PLANT
                                          D. n;^
                                            ' : \VN\ViKJi J -OF PLANT

-------
0
                                         AIR SAMPLE
                             LOCATION; CORNER OF 4th ST. AND
                                       HIGHLAND  AVE
                                       AUUNDEL ViLLAGL, ivlD.
                                 r\f-~i"'"- pr"^  ro  trt"'"'~
                                 iJi . I U.' I ' . .-. I /' . ;. I w i <-

                                 TI[/«iZ: I'' --^C- I:-"01.
4    6   8    10
TIME (M!N)

-------
                              AIR SAMPLE
                   LOCATION: PLAYGROUND ON NORTHBRIDGE 8

                             CANNERY \l(\ SN
0246


    TIME(MIN)
                       DATE: NOV. £5,
                              r, r f r i . r . i • v-  , . / . ,
                                   . . t • ". .< / U
                                           , 3

-------
    ©
\
                             AIR SAMPLE
                LOCATION: CONGO) PARKING LOT
                           -I/?. ;.-'E MC'RTi! OF
                           r-MC i.?!,viAZIN!i PLANT

                     DAT";: NO'/. ?,0r!£75

                     Til-.:-:: 5:00- G:CCP.;.".
                  n >-:T-1 :r , f -. •
                                 ' , : c\  ,  / .„.
                                   lev' .'. '. ' / ;ll
                          © DMN

                          © DEM

                          © DPN

-------
 o r;
 .-•;. s.
0    2
                                     AIR SAMPLE
                         LOCATION:  PMC DhV.AZINE  PLANT

                                    !00' \VLS1" OF
                             DATL:  NOV. !9» 1975
                          RC-SULT3:
                                   '; )  Di'.'il'! '  .;."' J /z ('•<•' «.»'
                                   •«. »^*          i *-
                                            ' -M
                                     i v. i • . \ .    l *i

                      _ t
8

-------


i
!
i

j



i



s
_
c
1
1
i

1
1
*l *
V
-JL
T r


}
.s

\


\
\l\ .
V -
'Wi
.L .-L
                              AIR SAMPLE
                 LGCATiQiv: DU.'ON'I' 1»LAHT
                            DELL, WEST VIRGINIA
                      "I" ' P, '1 f r ' <"'[ • '•*• ^ - I r\ • '•* ' ^ r •
                      I ; I . i ' • ,. ' •, ' • v' v  [•.-•••-.':.[,
                   RESULTS:
TIME (MlW)

-------
    Identification and Estimation of N-Nitrosodimethylamine and Other

          Pollutants in Ambient Air in the Baltimore,  MD

                     and Kanawha Valley Areas




EPA Contract No. 68-02-1228
                      E. D.  Pellizzart',  Ph.D.
                 Chemistry and Life Sciences Group
                   Research Triangle Institute
                          P. 0. Box 12194
           Research Triangle Park,  North Carolina  27709
                      Date:   January 5,  1976
Prepared for the Environmental Protection Agency,  Research Triangle Park,

North Carolina  27711

-------
Sampling Methods




     The sampling procedure employed for this study has been previously




described (1,2) which consisted of concentrating nitrosamines and other




organic vapors on a 1.5 x 6.0 cm bed of Tenax GC (35/60) in a glass




cartridge.  All sampling cartridges were preconditioned by heating to




275°C for a period of 20 min under a helium purge of 20-30 ml/min.




After cooling in precleaned Corex centrifuge tubes, the containers were




sealed to prevent contamination of the cartridge.  Sampling cartridges




prepared in this manner were carried by automobile or air freight to




the sampling site; 2-3 cartridges were designated as blanks to determine




whether any of the cartridges might have been contaminated by the pack-




ing and transportation procedure.  Cartridges containing known quantities




(100 and 300 ng) of N-nitrosodimethylamine (DMN) were prepared and carried




to and from the field, stored and the percent recoveries were determined.




     Ambient air samples were collected with Nutech Model 221-A AC/DC




portable samplers  (2).  In general, a sampling rate of 1 H/min/cartridge




was used throughout this study.




Gas-Liquid Chromatography/Mass Spectrometry Computer Analysis of Ambient




Air Samples




     The instrumental system (glc-ms-comp) used for the qualitative and




quantitative analyses of nitrosamines and other ambient air pollutants




and the inlet manifold used for recovering vapors trapped on Tenax GC




cartridge samplers were as described elsewhere (1,2).  The desorbed




vapors were resolved by capillary gas-liquid chromatography and mass




cracking patterns were automatically and continuously obtained through-




out the glc run with a Varian CH-7 gas chromatograph/mass spectrometer.




The cracking patterns and retention time data were accumulated on a

-------
magnetic tape deck and further processed by an on-line Varian 6201 com-




puter.  Computer programs (KOSB) were employed which converted the




acquired spectra Into a sequential series of mass spectra and were cor-




related to peak retention time on a total Ion current plot.  Data output




from the 6201 computer was provided In two forms:  (1) a teletype listing




which contained the mass spectrum number, number of peaks In the cracking




pattern, total maximum and minimum m/e peak intensity and standard devia-




tion from calibration m/e and (2) an electrostatic plot of total ion




current plots and/or normalized mass spectral.  Single ion plots (e_.£.




m/e 74) were obtained as an analog output.




     The operating parameters for the glc-ms-coiup system for analysis




of samples collected on glass cartridges from the Baltimore, MD area are




shown in Table 3.  Ambient air samples were analyzed on 55, 80 or 100




meter glass SCOT columns coated with either OV-101, OV-225 or DECS sta-




tionary phase, respectively.  The desorption of ambient air pollutants




including nitrosamines from the Tenax cartridge samplers was achieved




at 265-270°C.  A single stage glass jet separator interfaced the SCOT




capillary columns to the mass spectrometer and was maintained at 200°C.




     Identification of resolved components was achieved by comparing




the mass cracking pattern of the unknown mass spectra to an 8 major peak




index of mass spectra (1,2).  In several cases the identification was




confirmed by comparison with authentic compounds of the mass spectrum




and the elution temperature on two different columns.  Particular note




was made of the relationship of the boiling point of the identified




compound to its elution temperature and to its order of elution of cons-




tituent in homologous series since the OV-101 SCOT capillary column




separates primarily on the basis of boiling point.

-------
     For quantitative analysis, the mass spectrometer was set in the


single ion plotting mode whereby the selected master charge ratio was


recorded on analog output.  Quantitation of N-nitrosodimethylamine (by


monitoring only m/e 74) was conducted on a 55 meter glass SCOT capillary


coated with DECS.


     A standard curve for the response of the mass spectrometer set at


m/e 74 vs the concentration of DMN was prepared by introducing known


quantities of DMN vapor.  Synthetic alr-DMN vapor was synthesized and


specified quantities collected on Tenax GC cartridges.  By thermally


desorbing the cartridge and monitoring the m/e 74, responses vs concen-


tration were obtained.  Cartridge samplers containing unknown concentra-


tions of DMN were analyzed by monitoring the m/e 74 ion and obtaining the


quantity/cartridge from the standard curve.  Based on the volume of air


sampled and the breakthrough volume for DMN, the concentration of N-

                                           3
nitrosodimethylamine was calculated in ug/m  of ambient air.


Artifact Experiments


     The possibility of formation of DMN on the Tenax sampling cartridge


was investigated.  Since the Tenax cartridge sampler would concentrate


the dimethylamine if present in ambient air (breakthrough volume approxi-


mately 35 i at 25°C), it is conceivable that in the presence of NO , the


dimethylamine could become nitrosated to form DMN.  Two types of experi-


ments were conducted to either support or refute this possibility.  The


first set of experiments were conducted under laboratory conditions.


Synthetic mixtures of NO, water vapor, and air were prepared at known con-


centrations of 1, 10 and 250 parts-per-billion (in NO) in 7 £, glass bulbs.


Tenax cartridges were loaded with approximately 5 parts-per-million of

-------
dimethylamine and the NO  air vapor mixture was drawn through the cart-
                        A


ridge.  Cartridges were subsequently analyzed by single ion monitoring



of the m/e 74.  In another set of experiments, NO (-2 x 10   mole/min,



1 ppm) was introduced into a stream of laboratory air which was pulled



across a permeation tube containing dimethylamine at 1 Jl/min and into



the Tenax cartridge.  The sampling period was approximately 30 mln.  The



dimethylamine perineatdon- tube permeated at a rate of ~9 x 10   mole/min



(~4.5 ppm).  Thus, the amine to NO ratio was ~45:1.



     Experiments were also conducted during field sampling to demonstrate



whether an enhancement in the collection of N-nitrosodimethylamine could



occur above background when Tenax cartridges were either pre-loaded with



dimethylamine or when field air was drawn across a permeation tube con-



taining dimethylamine and into the Tenax cartridge.  The permeation tube



containing dimethylamine (~2.4 x 10   g/mln) was placed in front of the



glass fiber filter on the Tenax cartridge.  Therefore in these experi-



ments, the dimethylamine was introduced prior and after the glass fiber



filter.  All experiments were conducted in at least triplicate.  A total



of -120 Si of ambient air was sampled in all cases.

-------
Figure 1.         EAST BROOKLYN,
              BALTIMORE, MARYLAND
         CHESSIE
      COAL PIERS
                            CURTIS BAY
                                 SCALE: ONE INCH =0.5 miles

-------
                       Figure 2.   Map of FMC plant.
                                 *	x STONEHOUSE COVE

                           •'^Qlffdlokx'
                                                                             X= INCINERATOR  STACK
                                                                             SS= SAMPLING SITE
  1. Power House                     15<
1  2. Stack
•  3. Dapon Bldg.                     16.
  4. Refined Chemicals Bldg.         18.
'  6. Echion & Butoxide Bldg.         19.
  7. ?2S& Conveyor & Storage Bldg.   20,
  9. Diallyl Phthalate Bldg.         25,
10. Packaging Bldg.                . 26
11. Central Shop & Storeroom
11A. Maintenance Office Trailer
12. Fire Pump House                 30
13A. Warehouse
13B. Carpenter Shop                 34
13C. Warehouse & Shipping Dept.
14A. Storage                        39
14B. Storage                        40
.14C. Drum Recovery
Dapon Manufacturing  &   41.
Warehouse              43.
Warehouse              44.
Lab                    44.
Main Office Bldg.       47.
Gate House             48.
Booster Pump House     49.
Anhydrous Ammonia
Diraazine Control Rm.   51.
Lab                    52.
CO Compressor Shed     53,
Production Office       54,
Pyrethrum Refining     55.
Hydrogenators          59.
Nitroso                61,
Purification & Reco-   62
very                   63.
Valve House
Pump House
Storage
Storage
Pump House
Chloroformates
Sodium Condensa-
tions
Sodium Storage
Tedion Bldg.
LOckers
Lockers
Cafeteria
Paint Storage
Maint. & Prod.
Central Eng.
J. F. Wilson
Trailer
69. Hydrogenation
70. 7-OH Production
71. Control Lab
72. Incinerator Area
73. Elec. Control Rm.
74. 7-OK Warehouse
75. Effluent Control
    Rm.
76. Motor Control &
    Locker Rzi.
77. 7-OH Shop
78. Cl2 Control Rm.
79. Fire Pump House
80. Locker Rm.
81. Compressor Bldg.
82. Locker Rn.
86. Inert Gas Generator
87. Locker Ra.
88. Calgon Carbon Treat-
    ment Bldg.
89. Shop
91. Resin Semi-Works
    Plant
92. Pilot Plant
93. Elec. Control Ra.
95. Orvis Pilot Plant
98. Compressor Bldg.
CT. Cooling Tower
TF. Tank Farm
SS. Sub Station

-------
                         Table 1.   SAMPLING PROTOCOL  FOR BALTIMORE STUDY
Site Cartridge Replicates
FMC3
FMC
FMC
FMC
FMC
FMC
FMC
PS
PS
CP
CP
1
5
9
13
17
1
5
1
5
1
5
_
-
_
—
-
_
-
..
-
_
_
2
6
10
14
18
2
6
2
6
2
6
-3-4
-7-8
- 11
- 15
- 19
- 3 -
- 7 -
- 3 -
- 7 -
- 3 -
- 7 -
- 12
- 16
- 20
4
8
4
8
4
8
Time Period
11:00
3:00
7:00
11:00
3:00
11:00
3:00
10:00
2:00
9:56
2:10
AM -
PM -
PM -
PM -
AM -
AM -
PM -
AM -
PM -
AM -
PM -
2:
6:
10
2:
6:
2:
6:
1:
5:
1:
6:
50
50
PM
PM
:50 PM
50
50
50
50
50
50
46
00
AM
AM
PM
PM
PM
PM
PM
PM
Date
10/14/75
10/14/75
10/14/75
10/14 - 15/75
10/15/75
10/15/75
10/15/75
10/16/75
10/16/75
10/17/75
10/17/75
TL__Lm/e 74
(Quant.)
GC-MS-COMP (Qual
FMC (W of Dimazine Destructor)
Town of Fairfield
Near Memirac Corp.
FMC (SW of Dimazine Destructor)
11
11
"
Northbridge and Convery St.
it

1-2
1-2
V 2
1 9
1h * 2
1-2
1-2
if- 2
lb - 2









•>










2:00
3:45
8:20
11:50
1:55
6:35
6:35
1:48
3:59

PM -
PM -
PM -
AM -
PM -
PM -
PM -
PM -
PM -

4:
5:
10
1:
3:
8:
8:
3:
5:

00
45

PM
PM
:20 PM
50
55
35
35
48
59
PM
PM
PM
PM
PM
PM

11/19/75
11/20/75
11/20/75
11/24/75
11/24/75
11/24/75
11/24/75
11/25/75
11/25/75
m/e 74 (Quant.)
aParking lot




 Part of Artifact Experiment

-------
Table 2.  BREAKTHROUGH VOL FOR DMN
?F
50
55
60
65
70
75
80
85
90
95
100
105
110
2.2 g /cartridge
(1.5 x 6.0)
liters
385
332
280
242
204
224
163
156
148
127
107
93
79
2.93 g/cartridge
(1.5 x 8.0)
liters
513
493
373
322
272
244
217
207
197
170
143
123
103

-------
       Table 3.   OPERATING PARAMETERS FOR GLC-MS-COMP SYSTEM
  Parameter                                          Setting

Inlet-manifold
  desorption chamber                                 265°-270°
  valve                                              175°
  capillary trap - minimum                           -195°C
                   maximum                           +175°C
  thermal desorption time                            ~4 min
GLC
  OV-101 glass SCOT (100M)                           30-225°C, 4°C/min
  OV-225 glass (80M)                    '             80-210°C, 4°C/min
  DECS glass SCOT (55M)                              70-205°C, 4°C/min
  carrier (He) flow                                  1.5 ml/min
MS
  single stage glass jet separator                   200°C
  ion source vacuum                                  -2 x 10    torr
  filament current                                   300 yA
  multiplier                                         5.5
  scan rate, automatic-cyclic                        1 sec/decade
  scan range                                         m/e 20 -»•  300

-------
                              14
                                               30
20
, ** ,
1
6
TEMI
i 	
>ERATURE
1 	 i_
(°c)
164
i 	 i
212
t 	 i 	 1 	
. 2F
1 _. J
        12
15
18    21
                              24
                                    27
30    33
TIME (min)
                                                    36
                                                                                                 60
Figure 3.  Profile  of  ambient air pollutants in a sample taken during  the day on FMC parking lot.
           A 100M glass SCOT column containing OV-101 was used,  see  Table 3 for GLC/MS/COMP conditions.

-------
85
a
o
100


90-

80

70

60

50

40-




20


 10
                        air
                                                                                       34.5 min
                                                                                       (!96°c)


      Figure 4.  Profile  of  ambient air pollutants in a sample  taken during the day on FMC parking lot,

                 An 80M OV-225 glass SCOT column was used,  see  Table 3 for GLC/MS/COMP conditions.

-------
   lOOp

    90-
P
3  80

|  70

H  60H
LJ
|  50-

    40-
20

10
             air
               Kj
                                                               DMN
                                                                J_
                                                               26 mln
                                                               (ITB'c)
       Figure  5.  Profile  of  ambient air pollutants in a sample taken during the day on FMC
                  parking  lot.   A 55M DECS glass SCOT column was used, see Table 3 for GLC/MS/COMP
                  conditions.

-------
Figure 6.  Mass cracking pattern for N-nitrosodimethylamine
         CH
         CH.
              N-NO
            X
CH,
     N-N=0
CH

                                             3





                                            m/e 74
                                              -H, HNO









                                             2 = N = (





                                              m/e 42

-------
XDMN
too
90
I"
I70
H^
V) ,
Z 50
LJ
I30
£20
10
0
-


•







IOOMGSCOT OV225
70-225 »c

































.42





J

























AFMC4
IOOMGSCOT OV225
70-225ec
m/e 74



















"TT
10 20
BUI
3
0
HlHIl
I
0 40
i uiiniii im
«
50
m/p —
IH iii"'
0 7
3
8
illillili (Hi nil
0 90














































nnjim
i
iiiiini
o i;
.iiiiM
>o n
ranmi
50 !•<
100
	 1*.
riiinni
to




















10 2








1












42




• lit













iL

















m/e 74










m
0
m.
150 6
0 40
lititilii
e
T
0 7
50
m/o
;,i
D
80 90 110 120 130 MO
100
_ Irs. '
Figure 7.  Mass spectra of N-nitrosodimethylamine.  AFMC4 represents mass spectra from Figure 4.

-------
  lOOr

   90

   80-

<75  70-
z
      AFMC5
o  50
g  40
fee
GJ  30
E
   20
    10
                              m/e 74
                                         60MGSCOT DEGS
                         i"* •' "•
                               gii m.iln ••« ~IMtnil
         10 20 30 40
                         60 70  80  90
                      50
                     m/e
   110  120 130 140    160 170
100              150
   Figure   8.   Mass spectrum of N-nitrosodimethylamine, see  Figure 5
                for chromatographic  profile.

-------
3OOr-
                                                               2000 3000
      Figure 9.   Standard curve  for  N-nitrosodimethylamine

-------
  KXO
   9.0-
   ao-
   7.0 .
£
o:
U)
   50-
   3.0
   20
   1.0
                                                                                       26 mm
     Figure 10.   Single ion plot (m/e 7A) for N-nitrosodimethylamine, see Table 3 for  GLC/MS/COMP
                  conditions.

-------
   100
   90-
   ao-
   7.0
   eoh
UJ
F
   40-
   30-
   2.0-
   1.0-
      I
                                                                                        26 min.
         Figure 11.  Single ion plot  (n/e 74)  for N-nitrosodimethylamine (replicate cartridge  of  Fig.  12),
                     see Table 3  for  GLC/MS/COMP conditions.

-------
Table 5.  SAMPLING CONDITIONS AND CONCENTRATION OF N-NITROSODIMETHYLAMINE IN AMBIENT AIR
Date
10/14
10/15
10/15
10/16
10/17

Tine
(EOT)
11-2:50 PM
3-6:50 PM
7-10:50 PM
11-2:50 AM
3-6:50 AM
11-2:50 PM
3-6:50 PM
10-1:50 PM
2-5:50 PM
9:56-1:46 PM
2:10-6:00 PM
Temperature RH
Location (°F) (%)
FMC (P.
FMC (P.
FMC (P.
FMC (P.
FMC (P.
FMC (P.
FMC (P.
Sewage
Sewage
Chessie
Chessie
Lot)
Lot)
Lot)
Lot)
Lot)
Lot)
Lot)
Plant
Plant
Pier
Pier
83
85
74
65
61
85
83
72
72
55
55
40-50
45-50
65-85
90-97
97
40-50
40-50
45-57
45-50
88-94
94-100
Wind Molecular
Direc- Speed
tion (KTS) DECS
WNW 10 x
WNW 7 x
WSW 7 x
Calm
S
WSW 8-10 x
WSW 5-8 x
NNW 9-11
NNW 5-12
ENE 7-9 x
E 10-14 x
Verification DMN Concentration
OV-225 (ng/m3)
2,133
10,500 ± 1,167
(±11%)
x 1,375 ± 125
(±9%)
416
571
3,200
x 13,437 ± 937
(±7%)
trace
trace
909
x 84

-------
              Table 6.  SAMPLING CONDITIONS AND CONCENTRATIONS OF N-NITROSODIMETHYLAMINE
                                                                          Wind
                                                                                             DMN
                                                Temperature  RH
  Date
Time
Location
            Speed   Concentration
Direction  (Knots)     (ng/m3)
11/19/75  2:00 PM - 4:00 PM   FMC, 200 yd
                              W-NW of dimazine
                              thermal destruc-
                              tor

11/20/75  3:45 PM - 5:45 PM   Town of Fair-
                              field, 200 yd
                              from residen-
                              tial area,
                              Conoco parking
                              lot

11/20/75  8:20 PM - 10:20 PM  North of FMC,
                              near Memirac
                              Corp.

11/24/75  11:50 PM - 1:50 PM  FMC, SW of dia-
                              mazine thermal
                              destructor

11/24/75  1:55 PM - 3:55 PM       "

11/24/75  6:35 PM - 8:35 PM

11/25/75  1:48 PM - 3:48 PM  Northbridge &
                             Cannery St,
                             downwind of FMC
                                      65
                                    60-69
                                      57
                              56
                             57-73    SW-S
                              71
  S-SW
              3     32,000 ± 1,500
             3-6     1,950 -
 1,360 ± 510



20,000 ± 4,000



14,000 ± 200

26,000 ± 500

 7,600 -

-------
      Pollutants Identified in Ambient Air in Baltimore, MD Area
Chromatographic Peak No.
       Compound
           2
           5
           6
           7
           9
          10A
          15
          ISA
          21
          22

          27
          28
          29
          30
          33
          41
          42
          48
          52
          74
 trichlorofluoromethane
 methylene chloride
 chloroform
*l-chloro-2-methylpropene
*3-chloro-2-methylpropene
 1,1,1-trichloroethane
 carbon tetrachloride
 d ibromomethane
 trichloroethylene
 dichlorobutane isomer
*
 l-chloro-2-butene
*dimethylnitrosamine
 tetrachloroethylene
*dichlorobutene isomer
*2-chloro-l,3-butadiene (tent.)
 chlorobenzene
 dibromochlorofluoromethane
*trichlorobutane isomer
 1,1,3-trichloropropane (tent.)
 m-dichlorobenzene
 £-dichlorobenzene
 trichlorobenzene isomer
 Not previously reported.

-------
           0.0 ^.5 /?Od/7F 60
                     e  Ground level elevotion     603' CT

                     o  Methyl omine's went
                     o  Dimethyl formomide vent    753' 0"
                    Synthe»i» V«nt from
                    Dimethyl FTormamlde Ptont
                   BARGE IDADING

KANAWHA   RIVER
                                                     BARGE LDADING

-------
                                                       BAlfe8%5cESSES
                                                       Dimethylomine
                                                       Trimeth/lomlnl
                                                       Dl«thylomin*     kKEA 4
                                                                 TBNK CAR AND TRUCK CLEANING
                                                                 DlbutylomiM
                                                                 Morpholin«
                                                                 Oitthylomin*
                                                                 Dibutylomint
                                                                                       li
                                                              AREA 2
                                                               PROCESSES
     AREA 9
  S5-GAL. DRUMS
  STORAGE
  Diethylomint
  Dibutylamin*
.  Trwttiytoinint
  Morpholm*
        AREA I
CONTINUOUS PROCESSES
                                                                                                                            TRANSLDADING TANK CAR TO
     Dtttvtomln*
     Dlmtthylainln*
                                                 GAL.  AND SMALL CON-
                                                 TAINERS
                                                    Dielhylomine
                                                    Triethylamint
                                                    Morpholine
                                                    Dlbutyloniln*
                                                                                                                                            Tricthylamin*
                                                                                                                                            Morpholin

-------
~ "00
S.
LJ
10
in
LU
a:
5  501-
g
o
o
_j
     °0
                                                  10
                                                     13
                                                     1
                                                                              18
                                                                        22
 32
—t-
 44
—t-
 56
-t-
68
-t-
                      TEMPERATURE (°C)
 60      92       104      116              140

l5      i£~  ~~2i24~
                                                                                              152
                                                                                                      164
                                                                                      30
                         12
                                                          27
                                                   TIME (MIN)
                                                                                                  39
                                                                                                                 45
                                                                                                                         48
                                                                                                                                 51
                                                                                                                                  54
                                                                                                                                                 57

-------
  lOOr
   50-
-t

u
o
g
                                                                                                                             49
                                                                                                                              50
             32
            —I—
 44
-t-
                               56
                                        68
                                                 30
                                                         92
                                                                  104
                                                                           116
                                                                                 TEMPERATURE  (°C)
                                                                                    128      140      152
                                                                                        164
                                                                                                176
                                                                                                         188
                                                                                                                 200
                                                                                                                          212
                                                                                                                                   220
220

54
 220

IT
O1-
 0
                                        12
                                                 15
                                                          18
                                                                  21
                                                                           24
                                                              27       30
                                                               TIME (WIN)
                                                                                                    33
                                                                                                             36
                                                                                                                      39
                                                                                                                              42
                                                                                                                  45
                                                                                                                                                        51

-------
1111111111
                                                                                   I

                                                                                  111
1






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i
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62.
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?*
i
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i
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i i i i i i I l l
 ! IP"- !  i    \o   5>ft    "5O  ^0    :    feO
l  l  l  I                       50
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                                                         \io   \io  lie  \HO

                                                    \ko
                              rm/e

-------
         Table 1.  SAMPLING CONDITIONS AND CONCENTRATIONS OF N-NITROSODTMETHYLAMINE IN
                             AMBIENT AIR IN THE KAHAWHA VALLEY, WV.
   Site
   Location
Date
Time
Wind (Knots)/Temperature    ng/nr*
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
Belle, WV
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
S. Charleston
DuPont  (l)a         12/1/75  9:30 PM - 2:17 AM
DuPont  (2)          12/1/75  9:27 PM - 2:19 AM
DuPont  (3)          12/1/75  10:16 PM - 3:09 AM
DuPont  (4)          12/1/75  10:07 PM - 3:07 AM
DuPont  (1)          12/2/75  2:29 AM - 6:52 AM
DuPont  (2)          12/2/75  2:28 AM - 6:53 AM
DuPont  (3)          12/2/75  4:00 AM - 7:11 AM
DuPont  (4)          12/2/75  3:17 AM - 7:12 AM
DuPont  (2)          12/2/75  9:00 PM - 3:02 AM
DuPont  (3)          12/2/75  10:02 PM - 3:18 AM
DuPont  (4)          12/2/75  10:05 PM - 3:00 AM
Union. Carbide  (9)   12/3/75  2:41 PM - 6:01 PM
Union Carbide  (10)  12/3/75  3:12 PM - 5:12 PM
Union Carbide  (11)  12/3/75  3:36 PM - 6:27 PM
Union Carbide  (12)  12/3/75  3:38 PM - 5:28 PM
Union Carbide  (11)  12/3/75  6:33 PM - 8:53 PM
Union Carbide  (9)   12/3/75  6:16 PM - 8:19 PM
Union Carbide  (13)  12/3/75  5:51 PM - 7:56 PM
Union Carbide  (14)  12/3/75  6:15 PM - 8:40 PM
Union Carbide  (11)  12/3/75  6:33 PM - 8:53 PM
Union Carbide  (11)  12/3/75  8:28 PM - 10:30 PM
Union Carbide  (13)  12/3/75  8:03 PM - 10:17 PM
                              NW (2)/30-35°F             10.1
                              NW (2)/30-35*F              4.2
                              NW (2)/30-35°F              3.9
                              NW (2)/30-35°F          38.0 ± 6
                              SE- (4)/30°F             26.0 ± 4
                              SE (4)/30°F             12.9 ± 2
                              SE (4)/30°F                67.0
                              SE (4)/30°F             68.5 ± 5
                              SE (2)-calm/40-50°F        59
                              SE (2)/40°F             77.6 ± 6
                              SE (2)/40°F               103.0
                             WNW+NW (2)/50-55°F          <1
                             WNW-"NW (2)/50-55eF          NDb
                             WNW+NW (2)/50-55°F          13.6
                             WWH-NW (2)/50-55°F          11.6
                             NW+N (2)/45-50°F            ND
                             NW-»-N (2)/45-50°F            <1
                             NW+N (2)/45-50°F            ND
                             NW+N (3)/45-50°F            ND
                             NW-"N (3)/45-50°F            56
                             JMWE (3)/40-45°F           ND
                             N*NNE (3)/40-45°F        40 ± 2

-------
                                       Table ^  (cont'd)
   Site
   Location
 Date
Tine
Wind (Knots)/Temperature    ng/m"
S. Charleston  Union Carbide  (14)  12/3/75  8:47 PM - 10:44 PM
Belle, WV      DuPont  (5)          12/4/75  5:10 PM - 7:11 PM
Belle, WV      DuPont  (6)          12/4/75  3:26 PM - 5:24 PM
Belle, WV      DuPont  (7)          12/4/75  4:00 PM - 6:05 PM
Belle, WV
Nitro, WV
Nitro, WV
DuPont (8)
1-60 & WV25
1-60 & WV25
12/4/75  7:06 PM - 9:06 PM
12/5/75  11:58 AM - 3:48 PM
12/5/75  11:59 AM - 3:49 PM
                  N+NNE (3)/40-458F          ND
                  NE (2)-calm/54-60°F        ND
                  NE (2)-calm/60°F          980
                  calm (plumes/60°F         500
                     straight up)
                  NE (2)-calm/60°F          576
                  SW (10)/65°F               ND
                  SW (10)/65°F               ND
 See industrial plant map for precise location.
 ND - not detected.

-------
REFERENCES




1.   Pellizzari,  E.  D.   Development of Method for Carcinogenic Vapor




     Analysis in Ambient Atmospheres.   Publication No.  EPA-650/2-74-




     121, Contract No.  68-02-1228,  148 pp.,  July 1974.




2.   Pellizzari,  E.  D.   Development of Analytical Techniques for Measu-




     ring Ambient Atmospheric Carcinogenic Vapors.  Publication No.




     EPA-600/2-75-076,  Contract No. 68-02-1228,  185 pp.,  November 1975.

-------
DIMETHYLNITROSAMINE (DMN) SAMPLING PROGRAM






      BELLE, W. VA. - DEC. 1-5, 1975





   E. I. Du Pont De Nemours & Co., Inc.

-------
E. I. DU PONT DE NEMOURS & CO., INC. -.DMN SAMPLING PROGRAM

                            PAGE 1



Abstract

          Methods for determination of DMN in air have been studied
in cooperation with EPA contractors at Belle, W. Va.

          Laboratory studies show DMN is efficiently trapped by
5% KOH at ambient temperature.

          Analytical methods for trapped samples by Nitrogen
specific gas chromatography and gas chromatography-mass spectroscopy
are described.  Equivalent results are obtained from either method.

          Studies of trapping systems indicate that samples
taken at dry ice temperatures can give high DMN results when

-------
           T DE NEMOURS ft CODING.  - DMN SAMPLING PROGRAM

                           PAGE 2


Air Sampling for Dimethylnitrosamlne

    Method I - Dry Ice Trapping


         Air is drawn through a series of three cold traps at
1.8 -t/roin. for periods from 0.5 to 2 hours.  In the first trap
(ice-salt) the air is bubbled through an aqueous solution of
1056 KOH before it goes through the next two traps (dry ice-
acetone), each of which contain 0.5 ml 10$ KOH.

         After sampling is terminated the traps are thawed and
the contents of each trap are washed with distilled water  into
a common receiver (100 ml glass sample bottle).  The total
volume of the traps' contents and washings is 50-60 ml.  The
sample is analyzed immediately or frozen in dry ice pending
future analysis.


    Method II - Ambient Trapping


         Air is drawn through a series of two standard impinger
traps (500 ml capacity) containing 100 ml of IN KOH in each trap
at 5 -t/mln for 1 hour at ambient temperature.  The contents of
each trap are analyzed immediately or frozen in dry ice pending
future analysis.

-------
E. I. DU PONT DE NEMOURS * CO., TI?C. - DMN  SAMPLING PROGRAM

                            PAGE 3

                            CHART 1


                     DMN RECOVERY STUDIES


        EXPERIMENT                        % RECOVERY(1)

 100 ng DMN added to Trap 1               90% Trap  1
   240 S> of air sparged (4 fc/min.)        10% Trap  2

 20 nq DMN added to Trap 1                80% Trap  1
   240 S. of air sparged (5 jl/min.)        10% Trap  2

 20 ng DMN added to 100 ml IN KOH
   Frozen 1 week - one Sample             100%
   Room Temp. 1 week - Second Sample      100%

 10 ng DMN added to 100 ml IN KOH
   Frozen 1 week                           70"%

 20 ng DMN in 1 ml H20
   added to U tube; 300 £ of air          100% Trap 1
   pulled through at 4 Jl/min. *            10% Trap 2
             *300 SL blank (lab air) corresponded
              to none detected (<10 ng)
              NOTE:   20 ng in 300 liters of air = 22 ppt  (v/v)
  (1) Trapping Method II   (ambient),Analysis Method  B

-------
E. I. DU PONT DE NEMOURS ft CO.,  INC.  -  DMN  SAMPLING PROGRAM

                            PAGE 4

 Analysis for Dimethylnitrosamine

     Method A

          The contents of the sample bottle from the air sampling
 ar.e thawed and poured into a 125 ml separatory funnel (with
 Teflon stopcock).  Two 25 ml portions of distilled-in-glass
 CHsCl2 are used to rinse the sample bottle and are then added
 to the separatory funnel for extraction of dimethylnitrosamine.
 This 50 ml CH2C12 extraction is followed by a 25 ml CH2C12
 extraction.

          The CH2C12 extract is added to a Kuderna-Danish
 evaporator-concentrator, the receiver of which is in a water
 bath maintained at ~85°C.  When the volume of CH2C12 is 3 to 4
 ml, 1.5 ml nanograde benzene are added and the evaporation is
 continued until 1 ml benzene remains.  The benzene concentrate
 is then analyzed by alkaliflame ionization gas chromatography
 (selective for nitrogen containing compounds) with the following
 conditions:

       Gas Chromatograph - Perkin-Elmer  Model 900 equipped with
                           alkali flame ionization detector

       Column - 20' x 1/8" containing 20$ FFAP on Anakrom
                ABS, 80/100 mesh

       Injector port temperature - 200°C

       Detector temperature      - 230°C

       Column temperature        - 175°C isothermal

       Helium flow rate          - 28 ml/min.

       Sample injection size     - 5 Hi

       Dimethylnitrosamine retention time - ~7.5 rain.

          The lower limit of detection of dimethylnitrosamine by
 the Perkin-Elmer alkali flame ionization detector is approximately
 5 x 10"12g.

-------
E. I. DU PONT DE NEMOURS ft CO., INC.-  DMN  SAMPLING PROGRAM

                            PAGE 5

 Analysis for Dimethylnitrosamine

     Method B


          The contents of the traps are combined in a separatory
funnel and extracted 2 times with 100 ml of methylene chloride.
The combined methylene chloride extracts are passed through
approximately lOg of anhydrous Na2S04 (on a bed of cotton in a
funnel) to remove water.  Then the extracts are evaporated in a
beaker in a stream of dry N2 to ~10 ml before being transferred to
small calibrated vial where the evaporation is continued to a final
volume of 1 ml.   During the initial evaporation-concentration pro-
cedure the beaker is warmed slightly to prevent icing or water
condensation.
       Analysis of the CHsClg concentrate is accomplished by a
 Perkin-Elmer Model 900 coupled to a Du Pont Model "492 mass
 spectrometer.  The gas chromatographic conditions are:

       Column - 6' x 2mm i.d. glass packed with Tenax® - GC,
                60/80 mesh

       Column temperature - 100 °C isothermal

       He flow rate - 20 ml/min

       Jet Separator temperature - 250 °C

       Injection port temperature - 200°C

       Sample Injection size - 3^1

       Dimethylnitrosamine retention time - ~4 min.
          Dimethylnitrosaraine is monitored in the mass spectrometer
 at m 7^.  The lowest detection limit is 30 x Kr12g.
    e

-------
     E.  I.  DU FONT DE IfEMOURS ft CO.,  INC.  - DMN SAMPLING PROGRAM
                                 PAGE 6
                                 CHART 2

         DIMETHYLNITROSAMINE (DMN)  IN AIR - BELLE, W. VA.

                                        DMN        DMA    NOx (*)     Wind
  Date     Time       Location __ ppb        ppm    ppm      From mp!'
                                     (1)    (2)
12/1/75   8:35-    West Parking Lot  0.074 O.010 0.043  0.01-0.23  N.W. 0-
          9:35 pm                                        avg.0.08
12/1/75  10:35-    Plant Main Ent.    0.064 O.010 0.070  0.04-0.20  E    0-
         11:35 pm                                        avg.-0.o8
12/2/75   1:^6-    West Parking Lot  0.107 O.010 0.012  0.08-0.13  S.E. 3-
          2:37 am*                                       avg.-0.10
12/2/75   3:^5-    Cal.Ave.  & Wash.St.0.330     -     -     -        W  '  5
          4:45 am*
12/2/75   8:40-    S.E. Quadrant of  0.158 0.025  0.041  0.11-0.21  ESE  1-
          9:40 pm  Old Catalyst Plant0.019(3)            avg.-0.17
12/4/75   3:00-    #8 Pump Pit on    0.099O.010  0.050  0.03-0.11  S    1-
          4:00 pm*  Simmons  Creek                        avg.-0.07
12/5/75  11:00 am  Amines Vent       0.169   —   0.190  0.08-0.39  ESE  3
                                                         avg.-0.25
•Overlapped with Thermo Electron's times.
Notes
   (1) Trapping Method I (dry ice), Analysis Method A (N detector)
       Detection limit 0.001 ppb
   (2) Trapping Method II (ambient), Analysis Method B (GC/MS)
       Detection limit 0.01  ppb
   (3) Trapping Method II (ambient),  Analysis Method A (N detector)
   (4) Measured at Works Control Lab

-------
       E.  I.  DU PONT DE NEMOURS fr. CO., INC.- DMN SAMPLING PROGRAM

                                 PAGE 7

                                CHART 3
                           DMN ARTIFACT STUDIES
    _/ REAGENT CONG
    DMR            NO"
0.1 ml (Gas     0.1 ml (Gas
       Syringe)        Syringe)

100 -t 0.5 ppm  10 -t  10 ppm


100 t 0.5 ppm  100 I 0.1 ppm

100 £ 0.5 ppm  100 4, 1 ppm


100 -t 0.5 ppm  100 t 0.5 ppm


100 -t 0.1 ppm  100 £ 1 ppm


100 I 0.5 ppm  60 t Highway Air


None           60 t Auto Exhaust

None           200 -t Highway Air
  	DMN FOUND  (ug.)*
  DRY ICE TRAPSAMBIENT TRAPS
  AND WORK-UP  A  AND WORK-UP  3
10
                   0.02
0.01
J.W
(30 ppb in air)

<0.01,<0.01        O.01
 e>
 1
 (1.7 ppb in air)

0.03
(0.05 ppb in air)

0.01
(0.02 ppb in air)
0.44
(0.9 ppb in air)
                  <0.01

                  0.01
*GC/MS used for analysis

-------
        E.  I. DU PONT DE NEMOURS ft  CO.,  INC.  -  DMN SAMPLING PROGRAM
                                PAGE 8
                               CHART 4
                   DIMETHYLNITROSAMINE  (DMN)  IN WATER
Date
11/19/75
11/19/75
12/1/75
12/3/75
12/3/75
12/9/75
12/9/75
12/19/75
12/19/75
Time
8-4 shift
8-4 shift
2:30 pm
3:15 pm
10:00 pm
8-11 am
8-11 am
-
-
Location
WTP Influent
WTP Effluent
Kanawaha River @ Chelyan
(~4 miles upstream)
WTP Effluent
WTP Effluent
Kanawha River @ Chelyan
Kanawha River @ City bridge
(~9 miles downstream)
Kanawha River @ Chelyan
Kanawha River @ City bridge
DMN ppb
2.0
3.0
0.09
8.6; 5.1
4.1®
<0.0:^
0.03
0.08
0.07
                                                                     (1)
(1)  Method  A  -  Nitrogen detector gas  chromatography
(2)  GC/MS at  Du Pont
(3)  Aliquot of  sample analyzed by Thermo  Electron
(4)  Detection limit - 0.03 ppb

-------
DIMETHYLNITROSAMINE (DMN) SAMPLING PROGRAM





      BELLE, W. VA. - DEC. 1-5, 1975





   E. I. Du Pont De Nemours & Co., Inc.

-------
E. I.  DU PONT DE NEMOURS & CO.,  INC.  -.DMN SAMPLING PROGRAM

                            PAGE 1



Abstract

          Methods for determination of DMN in air have been studied
in cooperation with EPA contractors at Belle, W. Va.

          Laboratory studies show DMN is efficiently trapped by
5# KOH at ambient temperature.

          Analytical methods for trapped samples by Nitrogen
specific gas chromatography and gas chromatography-mass spectroscopy
are described.  Equivalent results are obtained from either method.

          Studies of trapping systems indicate that samples
taken at dry ice temperatures can give high DMN results when

-------
E. I. DU PONT DE NEMOURS ft CO., INC.  - DMN SAMPLING PROGRAM

                            PAGE 2


 Air Sampling for Dimethylnitrosamine

     Method I - Dry Ice Trapping


          Air is drawn through a series of three cold traps at
 1.8 Vmin. for periods from 0.5 to 2 hours.  In the first trap
 (ice-salt) the air is bubbled through an aqueous solution of
 10$ KOH before it goes through the next two traps (dry ice-
 acetone), each of which contain 0.5 ml 10$ KOH.

          After sampling is terminated the traps are thawed and
 the contents of each trap are \7ashed with distilled water  into
 a common receiver (100 ml glass sample bottle).  The total
 volume of the traps' contents and washings is 50-60 ml.  The
 sample is analyzed immediately or frozen in dry ice pending
 future analysis.


     Method II - Ambient Trapping


          Air is drawn through a series of two standard impinger
 traps  (500 ml capacity) containing 100 ml of IN KOH in each trap
 at  5 Vmin for 1 hour at ambient temperature.  The contents of
 each trap are analyzed immediately or frozen in dry ice pending
 future analysis.

-------
E. i. D'J POTT r^ ?;F.Mo;rps -•• co., T::C.  -  p'/n   SAMPLING PROGRAM

                            PAGE 3

                            CHART 1

                     DMN RECOVERY STUDIES


        EXPi:ray.:-::jT                         %
 100 ng DMN added to Trap 1                90% Trap 1
   240 I of air spargad  (4 5,/min.)         10% Trap 2

 20 ng DMN added to- Trap 1                 80% Trap 1
   240 i of air sparoed  (5 Z/min.)         10% Trap 2

 20 ng DMN1 added to 100 ml IN KOH
   Frozen 1 \:eek - one Sanple              100%
   Room Temp. 1 week - Second Sample       100%

 10 ng DMN added to 100 ml IN KOH
   Frozen 1 week                            70%

 20 ng DMN in 1 ml H20
   added to U tube; 300 i of air           100% Trao 1
   pulled through at 4 i/min. *             10% Trap 2
             *300 i blank (lab air) corresponded
              to none detected (<10 ng)
              NOTE:   20 ng in 300 liters of air =  22 ppt (v/v)
 (1) Trapping Method II   (ambient),Analysis  Method B (GC/MS)

-------
E. T. PU PONT DE NEMOURS fc CO.,  INC.  -  DMN  SAMPLING PROGRAM

                            PAGE 4

 Analysis for Dimethylnitrosamine

     Method A

          The contents of the sample bottle from the air sampling
 are thawed and poured into a 125 ml separatory funnel (with
 Teflon stopcock).  Two 25 ml portions of distilled-in-glass
 CffeCla are used to rinse the sample bottle and are then added
 to the separatory funnel for extraction of dimethylnitrosamine.
 This 50 ml CH2C12 extraction is followed by a 25 ml CH2C12
 extraction.

          The CH2C12 extract is added to a Kuderna-Danish
 evaporator-concentrator, the receiver of which is in a water
 bath maintained at ~85°C.  When the volume of CH2C12 is 3 to 4
 ml, 1.5 ml nanograde benzene are added and the evaporation is
 continued until 1 ml benzene remains.  The benzene concentrate
 is then analyzed by alkaliflame ionization gas chromatography
 (selective for nitrogen containing compounds.) with the following
 conditions:

       Gas Chromatograph - Perkin-Elmer  Model 900 equipped with
                           alkali flame ionization detector

       Column - 20' x 1/8" containing 20$ FFAP on Anakrom
                ABS, 80/100 mesh

       Injector port temperature - 200°C

       Detector temperature      - 230°C

       Column temperature        - 1?5°C isothermal

       Helium flow rate          - 28 ml/min.

       Sample injection size     - 5 nl

       Dimethylnitrosamine retention time - ~7.5 rain.

          The lower limit of detection of dimethylnitrosamine by
 the Perkin-Elmer alkali flame ionization detector is approximately
 5 x 10"  g.

-------
E. I. DU PONT PS NEMOURS ft CO., INC.- . DMN  SAMPLING PROGRAM

                            PAGE 5

 Analysis for Dimethylnitrosamine

     Method B


          The contents of the traps are combined in a separatory
funnel and extracted 2 times with 100 ml of methylene chloride.
The combined methylene chloride extracts are passed through
approximately lOg of anhydrous Na2S04 (on a bed of cotton in a
funnel)  to remove water.   Then the extracts are evaporated in a
beaker in a stream of dry N2 to ~10 ml before being transferred to
small calibrated vial where the evaporation is continued to a final
volume of 1 ml.   During the initial evaporation-concentration pro-
cedure the beaker 'is warmed slightly to prevent icing or water*
condensation.

       Analysis of the CH2C12 concentrate is accomplished by a
 Perkin-Elmer Model 900 coupled to a Du Pont Model "^92 mass
 spectrometer.  The gas chromatographic conditions are:

       Column - 6' x 2mm i.d. glass packed with Tenax® - GC.
                60/80 mesh

       Column temperature - 100°C isothermal

       He flow rate - 20 ml/min

       Jet Separator temperature - 250°C

       Injection port temperature - 200°C

       Sample injection size - 3ul

       Dimethylnitrosamine retention time - ~4 min.

          Dimethylnitrosamine is monitored in the mass spectrometer
 at m 74.  The lowest detection limit is 30 x lQ-12g.
    6

-------
     Cl.  1.  U(J
                                 PAGE 6

                                 CHART 2


         DIMETHYLNITROSAMINE (DMN)  IN AIR - BELLE, W. VA.


                                        DMN        DMA    NOx        Wind
  Date  •   Time       Location __ ppb        ppm    ppm      From rr^
                                     (1)    (2)

12/1/75   8:35-    West Parking Lot  0.074 O.010 0.043  0.01-0.23  N.W. C
          9:35 pm                                    '    avg.0.08

12/1/75  10:35-    Plant Main Ent.    0.064 O.010 0.070  0.04-0.20  E    C
         11:35 pm                                        avg.-0.08
12/2/75   1:46-    West Parking Lot  0.107 O.010 0.012  0.08-0.13  S.E. 3-
          2:37 am*                      -                 avg.-0.10

12/2/75   3:45-    Cal.Ave.  & Wash. St. 0.130     -                    W    5
          4:45 am*

12/2/75   8:40-    S.E. Quadrant of  0.158 0.025  0.041  0.11-0.21  ESE  1-
          9:40 pm  Old Catalyst Plant0.019(3)            avg.-0.17

12/4/75   3:00-    #8 Pump Pit on    0.099
-------
       E.  I.  DU PONT DE NEMOURS fr CO.,  INC.- DMN SAMPLING PROGRAM

                                 PAGE 7

                                CHART 3
                           DMN ARTIFACT STUDIES
      REAGENT CONG.
    DMA
    NO
0.1 ml (Gas     0.1 ml (Gas
       Syringe)        Syringe)

100 £ 0.5 ppm  10 -t  10 ppm
100 t 0.5 ppm  100 t 0.1 ppm

100 -t 0.5 ppm  100 £ 1 ppm


100 t 0.5 ppm  100 -t 0.5 ppm


100 *• 0.1 ppm  100 £ 1 ppm


100 -t 0.5 ppm  60 I Highway Air
None

None
60 £ Auto Exhaust

200 I Highway Air
                                                     DMN FOUND (ug.)*
DRY ICE TRAPS   AMBIENT TRAPS
AND WORK-UP  A  AND WORK-UP
                            0.14
                            10
                            (30 ppb in air)

                            
-------
                                 PAGE 8
                                CHART 4
                   DIMETHYLNITROSAMINE  (DMN)  IN WATER
Date
11/19/75
11/19/75
12/1/75
12/3/75
12/3/75
12/9/75
12/9/75
12/19/75
12/19/75
Time
8-4 shift
8-4 shift
2:30 pm
3:15 pm
10:00 pm
8-11 am
8-11 am
-
-
Location
WTP Influent
WTP Effluent
Kanawaha River @ Chelyan
(~4 miles upstream)
WTP Effluent
WTP Effluent
Kanawha River @ Chelyan
Kanawha River @ City bridge
(~g miles downstream)
Kanawha River @ Chelyan
Kanawha River @ City bridge
DMN ppb
2.0
3.0
0.09
8.6; 5.:
4.1®
<0.0^
0.03
0.08
0.07
                                                                     (1)
(1)  Method A -  Nitrogen  detector  gas  chromatography
(2)  GC/MS at Du Pont
(3)  Aliquot of  sample analyzed  by Thermo Electron
(4)  Detection limit - 0.03 ppb

-------