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—
-------
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
-------
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^ .cici-HO-HO mixture in room sir
at normal humidity. When 1 ppm dijTiethylamine war? mixed with 1 ppin MO.
and 4 ppm NO in dry nitrogen, the amine reacted at a rate of about 1
percent per minute. Assuming the product to be entirely N-nitroso
diinethylaminc allowed the calculation of an upper limit for the rate
of nltrosation by either KO or HO., . These upper limit rater; arn. too
slow to allow for an appreciable degree of riitroaation by NO or KG in
real r.?.ibic-:nt atruosphGret.;.
-------
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 —
-------
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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Bottom - Sane sample as top, photolyrcd one hour with
ultraviolet fluorescent li^ht filtered through
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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-
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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
rn ni nn IIIIIIIIIMIII!MII!':II
i i i i i i i i i
i t i nn • i i
i
1
i
j
!
i
•
i
i
i :;
i .. i ,! !!
I iM:1:-:!;:::!.:1::-;1:1.,::1 v:
' 1 1 1 i • . '
i ii i
62.
» **l"" ** ^ »
?*
i
'
i
:,!
'V I "| 1 1 i' 1 1 1 1 I I I I ' « I I ' '
i i i i i i I l l
! IP"- ! i \o 5>ft "5O ^0 : feO
l l l I 50
i in
l li mi
\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
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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
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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
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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)
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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
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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
------- |