A P P L I C A T I O N OF R E A L - T I M E

MASS S P E C T R O M E T R I C T E C H N I Q U E S
TO E N V I R O N M E N T A L O R G A N I C G E O C H E M I S T R Y
II. O R G A N I C M A T T E R IN
SAN F R A N C I S C O BAY A R E A W A T E R 1
B. R. SIMONEIT
Space Scwnce Laboratory
University (f Califi,rnm
Berkeley, Calif. 9.¢720
D. H. SMITH~
Oreanic Geochemistry Un#, School of Chemistry
University of Bristol
Bristol, BS8 ITS, England
G, EGLINTON
Organic Gevchemist~\v Unit, School of Chemisti2v
Uniw,rsiO"~?]Bristol
Bristol, BS8 ITS, England
A. L. BURLINGAME3
Space Scwnce Laboratory
UmversiO"(f CahJbrnia
Berkel©,, Cal(fi 94720

A preliminary study was made of the solvent-soluble (organic) matter passing

through a fine fritted filter in samples of water taken from the San Francisco and
San Pablo bays, the Carquinez Strait, and an estuary in the confluence of the Sacra-
mento and San Joaquin rivers. The petroleum ether extracts (ranging from 2.5 to
102 #g/liter) were analyzed using gas chromatography, computer-coupled gas
chromatography/mass spectrometry, and high-resolution mass spectrometry. The or-
ganic compounds identified in these extracts are quite diverse and consist mainly of
hydrocarbons from various sources. Some phthalate esters occur at various sampling
sites. The conclusion is that the techniques of gas chromatography/mass spectrometry
and high-resolution mass spectrometry are ideally suited to the assessment of some
of the potential interactions of pollutants and other organic compounds in the
aquatic environment.

Studies of trace organic constituents in sea and fresh waters have indicated the neces-
sity for the use o f analytical methods which not only have high sensitivity but, as well,

1For part I., see Simoneit et al. (1973).

2Present address: Department of Chemistry, Stanford University, Stanford, Calif. 94305.
3John Simon Guggenheim Memorial Fellow, 1970-72.

193

Archives of Environmental Contamination and Toxicology,

Vol. 1, No. 3, 1973, © 1973 by
Springer-Verlag New York Inc.
194 B.R. Simoneit et al.

provide reliable structural information on components of complex mixtures. In par-

ticular, the solubility of crude oils in sea water has been examined (Boylan and Tripp
1971), and certain hydrocarbon fractions and compound classes in crude oil were tbund
to have pheromonal activity with certain fauna (Boylan and Tripp 1971, Boylan
197t). Other effects of various types of pollutants on the biota in natural waters and
on water quality have been reviewed by Ciaccio (1971) and Hood (1970).

In another publication, Simoneit e t aL (1973) describe the utility of the various mass
spectrometric techniques in studying organic compounds present in the environment.
In the present paper, the authors discuss, in more detail, preliminary results obtained
in examining samples of water taken at various locations in the San Francisco Bay
Area. The intent of the present study was to determine what chemical information the
application of the various analytical techniques mentioned below can yield and whether
or not they can be utilized to elucidate some general conclusions regarding the origin
of a specific water sample (i.e. deep vs. shallow, clear vs. turbid). It was anticipated
that the application of these techniques would be particularly useful in the comparison
and intercorrelation of an environmental sampling grid. Most studies of water pollution
problems employ only a single analytical technique, such as gas chromatography ~Scher
1970) or gas chromatography/mass spectrometry (Garrison et al. 1970). It was of par-
ticular interest to determine whether or not the combined use of certain sensitive mass
spectrometric methods in such studies can provide additional information to gas
chromatography.

The present paper summarizes results from a preliminary, study of the "dissolved"
organic matter [that is, the solvent-soluble matter (>Cls) which passes through a
fine fritted Buchner funnel (pore size ca. 5 /xm)] in water samples taken at various loca-
tions in the San Francisco and San Pablo bays, in the confluence of the Sacramento
and San Joaquin rivers, and in the strait which connects this confluence with the San
Pablo Bay. These water samples come from a variety of sites, including some near
oil-refining facilities, domestic-waste discharges, and bay (shallow and deep) and
estuarine areas; they consist mainly of scattered " g r a b " samples.

The water samples were collected, extracted with petroleum ether, and analyzed
for extractable organic matter by means of combination of gas chromatography (GC),
computer coupled gas chromatography/mass spectrometry (GC/MS) (Smith et al. 1971)
and real-time high-resolution mass spectrometry (HRMS) (Burlingame 1968, Burlingame
t970, Burlingame e t al. 1970). The extract (only compounds >Cls ) yields ranged from
2.5 to 102 #g per liter.

Methods and apparatus

The methods used were ones that had been tested extensively in connection with
geochemical (Eglinton and Murphy 1969) and lunar (Simoneit and Burlingame 1972,
 Mass Spectrometric Identification of Organic Matter in S. F. Bay Water 195

Simoneit and Flory 1971, Simoneit 1973a) analyses. In this case, the extraction
technique was identical to that in the standard method of oil and grease analysis (com-
pounds >Cls ) in water (Taras et al. 1971). Each piece of glassware, including the
sample bottle, was cleaned with chromic acid solution, thoroughly rinsed with distilled
water, dried, and rinsed with benzene and methanol (3:1 by volume, nanograde purity).
The sampler consisted of a weighted holder fitted around a narrow-mouth glass bottle
(ca. 4 - l i t e r ) a n d was suspended from a rope marked in meter increments. After sub-
mersion to the desired depth, the bottle was opened and closed for sampling by a lead
plug, activated by a pull-string. To prevent post-collection modification of organic
material, 25 ml of concentrated sulfuric acid was added to each sample bottle as an
algicide. 4 Upon sample recovery, the bottles were sealed with a Teflon-lined cap and
kept refrigerated (ca. 4°C) until analysis (within 24 hours of sampling). After filtration
through a fine glass frit (ca. 5 bern pores), each water sample was extracted with two
300-ml portions of petroleum ether (nanograde purity) in a separatory funnel. Each
petroleum ether extract was washed with 200 ml of distilled water and concentrated
to approximately 2 ml on a rotary evaporator (water bath at 30°C): then, the concen-
trated extract was evaporated to dryness under a stream of nitrogen, weighed, and redis-
solved in n-heptane for analysis. The resulting extracts were all subjected to GC
analysis without separation or derivatization.

The results obtained in the initial GC analyses and the amount of total extracts were
used to determine which of the following mass spectrometric techniques would yield
the most chemical information (Simoneit et al. 1973). Low or high amounts of
unresolved (by GC) extract were subjected to HRMS in order to provide the maximum
information regarding the suite of elemental compositions and component functionalities
present in such mixtures. Those extracts which yielded relatively well-separated GC
peaks and which also consisted of sufficient sample were subjected to GC/MS. The
low amount (<100 beg) of extractable material and/or the complexity of the mixture
dictated the use of HRMS in the case of water samples from sites 11 and 12 (as well
as from sites 3, 5, 8 - 1 0 , 14, and 16). In spite of their complexity, the presence of
well-defined GC peaks and sufficient amount of extractives in samples from sites 13
and 15 permitted GC/MS analysis of these extracts, and allowed correlation of their
analytical results with those of extracts, from other samples, which exhibit similar GC
patterns. The small amounts (<10 beg) of extract in the sample from site 4 and in the
blanks allowed only GC analyses (at least, to date).

The GC analyses were made with a Perkin-Elmer Model no. 900 gas chromato-
graph equipped with a flame-ionization detector and a stainless-steel column (10 ft
x 1/8 in.), packed with 3 percent by weight of OV-1 on 100/120 mesh Gas Chrom
Q; its operating conditions were: programmed from 100°C to 275°C, at 8°/min: helium-

4Sulfuric acid probably is the most organically "pure" algicide, although it can cause hydrolysis of certain
esters, etc.
196 B.R. Simoneit et al.

carrier gas (60 mi/min.). For GC/MS analyses, a modified Perkin-Elmer Model no.
270 gas chromatograph/mass spectrometer linked online to an XDS Sigma-2 computer
(Smith e t al. 1971) was used. High-resolution mass spectrometry was accomplished
using a GEC-AEI MS-902 mass spectrometer linked online to an XDS Sigma 7 com-
puter (Buflingame 1968, Burlingame 1970, Burlingame e t aL 1970). The samples were
introduced via a ceramic, direct-inlet probe into the ion source, operated at normal
conditions (Burlingame 1968, Burlingame 1970, Burlingame et al. t970). Representa-
tive high-resolution mass spectral data are presented as heteroatomic plots (Burlingame
and Smith 1968).

W a t e r - s a m p l i n g details

Grab samples of water were taken with the sampler at the 13 sites shown in Fig.
1 which is a simplified map of the San Francisco Bay Area. The samples were taken
at depths varying from 0.5 m to 8 m in the period of May 30, 197t, to September
1, 1971, (Table I). The sites were chosen to be representative of a variety of aquatic
environments.

Results and discussion

A summary of the types of organic material found in the petroleum ether extract
of the individual water samples is given in Table I and some selected representative
GC traces are shown in Fig. 2. The subsequent discussion is concerned only with results
which are representative of the scope of application of GC/MS and HRMS to the iden-
tification of molecular compositions of complex mixtures. The extractives obtained from
samples, at all sites, consisted predominantly of cyclic and acyclic hydrocarbons; how-
ever, there are large variations in relative amounts of the various structural types of
compounds present. For example, the site 3 extract consists mainly of n-alkanes, the
site 13 extract consists predominantly of steranes, and the site 15 extract contains a
large proportion of unsaturated hydrocarbons. The biogenic odd-over-even predomi-
nance in the alkane distribution about C2o with a maximum at pentacosane is found
for the extracts from site 5, 7-12, and 14-16; this pattern is not evident in the site
13 and 17 extracts. The abundance of oxygenated organic matter is low in all extracts,
and significant amounts (in terms of relative abundances, only) of ions containing ni-
trogen, sulfur, or chlorine are not evident in the mass spectrometric data. In several
extracts, minor amounts of ions containing silicon are detectable.

The salient features of the GC/MS data for the extract from site 15 are shown in
Fig. 3. The total ionization sum plot (Fig. 3a) indicates a series of peaks superimposed
on a complex "'hump" due to the mixture complexity (see Fig. 2). Although the mass
spectra essentially all correspond to mixtures of compounds, other techniques of com-
puter-aided predigestion of mass spectral data are available which aid in identifying
 Mass Spectrometric Identification of Organic Matter in S. F. Bay Water 197

San Pablo Bay \ Vallejo

15
Pittsburg
Martinez C~ll ond 12
Antioch

I
Richardsonl
Bay Berkeley

j , Oakland
San
"O
Francisco

J ~
San Mateo ~__.3 ~,
agward

Palo A to

Fig, I. Map of the sampling sites in the San Francisco Bay Area
 Table I. Source and Description of WaterSamples, Yield of Organic
Extract, and Proximate Composition of the Extracts
Site number Sampling site, physical appearance,
(see Fig. 1) and depth and time of sampling
Richardson Bay mouth; turbid a (1 m)
(May 30, 1971; 10:15)
Incoming tide; clear (1 m)
(May 30, 1971; 14:30)
Upper Richardson Bay; very turbid (0.5 m)
(May 30, 1971; 18:30)
South San Francisco Bay; very turbid,
high red algal content (3 m)
(July 24, 1971; 17:15)
Ship channel under San Mateo Bridge;
turbid (3 m)
(July 26, 1971; 18:10)
Near shore south San Francisco Bay;
turbid with red algae (2 m)
(July 26, 1971; t8:25)
10 Near shore, off Castro Rocks;
turbid (3 m)
(August 9, 1971; 24:00)
11 and 12 San Joaquin River, very turbid:
downriver flow (both 6 m)
(August 22, 1971; 20:25)
13 San Pablo Bay; slightly turbid (7 m)
(September 1, 1971; 12:25)
Extract
Yield, /xg/1 Proximate composition
12 Alkanes (>C24) and major peak (~C~s) b,d
2.5 Similar pattern as for 3 b,d
t~
25 Similar pattern as for 3 but suppressed by
large peak of pentacosane b,d
37 Complex mixture, large peak (silicone O
oil) predominating b,af
20 Complex hydrocarbon mixture, two large
peaks (-C,.,0 and ~-C2a) predominating;
similar pattern as for 7 b,d
12 Complex hydrocarbon mixture, large
peak (-C25) predominating; similar
pattern as for 7 b,d
28 Complex hydrocarbon mixture, two large
peaks (-C20 and -C2s) predominating;
similar pattern as for 8 b,d
40 and 60 Complex hydrocarbon mixture; yield
very similar GC patterns; large
peak (C2a) predominating b,c,d
32 Hydrocarbons, lanostane predominating;
alkanes Cis-Ca2 b,c
 Extract
Site number Sampling site, physical appearance,
(see Fig. 1) and depth and time of sampling Yield, /xg/1 Proximate composition

14 Carquinez Strait: turbid (8 m) 25 Similar pattern as for 13; hydrocarbons, g

(September 1, 1971; 12:55) lanostane predominating but less intense:
©
alkanes IC~e-C.'3a)b,d
15 Selby, at refinery docks; light surface 60 Complex mixture with major series of
oil film, turbid (2 m) n-alkanes predominating (~C~5-Ca4);
(September 1, 1971; 13:20) bimodal with maxima at ~C~.~ and
~C,_,< olefins b,c,
16 Shallow cove; high green algal content, 102 Very complex hydrocarbon mixture: ga

very turbid (1 m) one peak (--C~0) predominates above

(September I, 1971: 14:45) bimodal pattern: no homologous o
series stand out b,d o
Richmond at refinery docks: tanker 25 Complex hydrocarbon mixture; several C/Q
17
pumping bilges: turbid (0.6 m) peaks predominate but no series is
(September I, 1971; 15:15) evident b,d
6 Blank (petroleum ether extraction Single peak (~ methyl palmitate)b
solvent: I liter used per sample) 7"
18 Blank (distilled water; one gallon) Mainly alkanes ('-Cis-Ca4) with three
other predominant peaks (not present
in samples) b
1 and 2 Procedural blanks Similar to 6 b ,<

g~
a Judgments of turbidity are subjective only.
b Determined by gas chromatography (GC).
Determined by gas chromatography/mass spectrometry (GC/MS).
d Determined by high-resolution mass spectrometry (HRMS).
rid
'.D
200 B . R . Simoneit et al.

Site 3 Site 13

8
g n-C28
Alkane
tr
nAI-Cka24el,,l~ nAI-Cka32
e
V ~ a c k g round
/~ ackground

i~ Site15
n-C28
P,
0~ L~Jv AIk~ne n ~ n e
If /'Backgro;nd

~ ~16 Alkane

Site 12 Site 17

n~;24 f! 'L
c
o Alkane~)~J ~ n ~ ~ kane
nc
IV Alkan4e n-C32AIkane
f n-C32Alkane
~ackground
C, ,,ne ~ / n-C16Alkane
Time Time--
(Conditions: 10 ft x 1/8 in. stainlesssteel column, packedwith 3%OV-1 on 100-200
meshGaschromQ, programmedfrom 100 - 275°Cat 8°/rain and usinghelium carrier
gasat 60 ml/min.)
Fig. 2. RepresentativeGC traces for extracts obtained from water samples.
 Mass Spectromelric Identification of Organic Matter in S. F. Bay Water 201

SlS

, r, 1,1,1,1,1,1 i, i, I , i, i, i, i, I , i, i, i, r ,i ,F ,i ,TI r-), i, i, i,1,[, F, i, i, i ,[rrTl~ i , i,[, i, i, i, i, 1 , r, i~l~,l,l,i i,i, i i i,i, I , i, i,i, i, I , i, i, 1, i, l, I , i, iyi I,F,IF,I i,

SIS
= 88492

I Mt~ 55 ~o

1~ 20 ~0 I0 50 ~0 70 8o 90 100 110 1~11 ]3o 140 150 lgo

- zzse~

I ~/E= 14900
X M/E; 16100

12 5
5~'~5 st eS= 315~1

77 S IS

o~o Ioo 15o ~oo ~5o 3o11

Fig. 3.GC/MS data for the extract from water sample obtained from site 15:
a) Total ionization sum plot;
b) m/e 55 and m/e 57 sum plot:
c) m/e 149 and m/e 167 sum plot:
d) mass spectrum scan 73;
e) mass spectrum scan 77.
202 B.R. Simoneit et al.

major contributors to individual mass spectra (Smith et al. 1971). The variation in
intensity of a particular m/e value can be plotted vs. time, yielding a fragment-ion
chromatogram (Hites and Biemann 1970). The ~/e values are chosen to be characteristic
of a homologous series of compounds (e.g., m/e 74 for methyl esters of fatty acids).

The mass chromatograms (Hites and Biemann I970) of m/e 55 and m/e 57 are pre-
sented superimposed in Fig. 3b, making it particularly simple to identify large ratio
changes between the alkane and alkene contributors. The m/e 57 ion is more intense
than the m/e 55 ion in the case of any alkane but these relative intensities are reversed
for alkenes. It is of interest to note that each of the m/e 57 peaks align with distinct
peaks in the total ionization plot (Fig. 3a). The latter peaks are alkanes, as substantiated
by the individual mass spectra [ e . g . , Fig. 3e fits the fragmentation pattern of
n-heneicosane (C21H44 , M+ 296) quite well although minor contributions from other
ions are present]. The presence of alkenes is indicated, for example, in scans 73 (Fig.
3d) and 75 where the intensity of m/e 55 is greater than m/e 57 (cf. Fig. 3b). The
scan 73 spectrum appears to arise from a mixture of at least two c o m p o u n d s :
heneicosene (C 21 H42, M+ 294) and heneicosadiene (C21 H4 o, M+ 292).

Mass chromatograms of m/e 74 (McLafferty rearrangement of methyl esters of normal

carboxylic acids) and m/e 98 (rearrangement ion of methyl esters of ~,w-dicarboxylic
acids) do not exhibit peaks above the baseline, indicating that these compounds are
not present in this extract. Since the extract mixture was not derivatized, free carboxylic
acids are not detected by this method.

Phthalate ester spectra usually exhibit an intense m/e 149 ion (CsHsO3) which is
a sensitive, characteristic peak for this class of compounds (cf. Fig. 3c). Examination
of the mass spectra at scans 59 and 66 indicates two isomers of dibutyl phthalate,
while scan 89 fits the fragmentation pattern of a diheptyl phthalate and scans 101-103
fit the fragmentation of dioctyl phthalate.

For mixtures exhibiting distinct GC peaks, high quality mass spectra of the
individual components are obtained by the GC/MS technique. The sample from site
13 serves as an example (cf. Fig. 2). The total ionization sum plot (Fig. 4a) is dominated
by a major peak maximizing at scan 163 (of. Fig. 4b). Computer analysis of these
data with a compound classifier program (Smith 1972, Chang et al. 1973) fit the scan
163 spectrum to a sterane of composition C30H54 and molecular weight 414. This spec-
trum matches that of authentic lanostane (structure A, below) very well. This compound
could be an altered algal or bacterial component because unicellular organisms would
pass the fritted filter used before the extraction. At present, the source of this compound
is unknown.
 Mass Spectrometric Identification of Organic Matter in S. F. Bay Water 203

HRMS ana!ysis of total extract mixtures yields specific data, in terms of elemental
compositions and high accuracy, for all ion intensities in the spectrum. Accurate mass
measurement allows determination of the heteroatomic content as well as the degree
of unsaturation, including cyclic and double bonds. Polar or low volatility compounds~
which do not pass through GC columns, can be detected. Many peaks in such total
extract analyses cannot be correlated to their parent compounds and original sources
(e.g., C19H3703 and C17H3303 in the C/H O3 plot of Figure 5) but they are a good
indication of the range of compound types present. The HRMS data for the sample

T17sTl~

163 ~ 12
X 5 - ~0 559 81130g

X5

ill;. i I1.1 . rL. i i i . , i !.l ; i . ~T.~.r , . i I, . i I T ~ N ' r ; I

ii. IL~..~I
, i , i
050 ~rlo isu 2r~o ~SrJ 31~o ~50 ~00

Fig. 4. GC/MS data for the extract from water sample obtained from site 13:
a) Total ionization sum plot;
b) mass spectrum scan 163
204 B . R . Simoneit et al.

, ~ 30 SI/PETETH6REXT

I
3,7 ~,9 ~/11 ~,1~ 1~15 8'17 S/19 ~01~1 11;23 1212~ 13/27 14/2U 15/31 1~/3~ 17/35 18/~? 1~l~9 20~41 21;43 22¢45 2]/2~ 24~4~ 25/5] 2~]~ 27155 2~/57 2~/59 3O/G1 31,~S 32/B5 33/~7 ~4/~9 35,71

~o mo ~ ~ z ~ ~ o ~ o ~50 4 4~0 s

7¢I 8/2 915 I0?7 11~9 12qI T3/IS T4115 15t17 lG/~9 17121 181~3 I~/2~ 210127 ZII29 22131 Z3133 24/35 25,37 2G139 27/41 28143 2~114530/47 31/4B 32/51 $3~53 34155 35/57 3G159
I
50

25 37 a*9 5]II G]13 ?'~I5 8lIT ~19 ~13'?) 1T¢23 12,25 135?2 147~ 15(3I tG;33 17t35 18/57 19;3g 2014t Zltl3 22]4~ 23147 ~0~9 SS/M 78]53 77~g 78~57 21~59 SO'GI 31~g3 t2JG5 33ff~734~G9

510 '10 ~I0 ZJO 2510 310 310 ~0 ~0 5JO

50 ~00
,I0

0/I 1,32,53;7 l~g 5/11 °H3 ?¢158117 Otl~ I0/2111/2312125 Taz2714/2915t31 IG/33 I?/35 Igt3719~3921]/~121/4322/4523~4724'4925,5I| 2S,S'I 2h552~:571~5E 30~a131/63 32;651
~n ~oo Ts~ k ~s0 3 o a~n 4~n ,~u 5oo

Fig. 5. Partial high-resolution mass spectral data for the extract from the water sample obtained
from site 17

from site 17 (Fig. 5)5 will serve as an example. The C/H data (hydrocarbon ions, top
plot) consist mainly o f hydrocarbons o f the series CnH2n+2 to CnH2n. 1 o for n = 4-29,
not every homolog being present. The polynuclear aromatic hydrocarbons are present

5Only the plots containing a major fraction of the total--ion current are shown: the minor peaks due to
13C, higher degrees of unsaturation,and higherheteroatom content are not shown.
 Mass Spectrometric Identification of Organic Matter in S. F. Bay Water 205

in minor amounts for the series CnH2n_12 to CnH2n_16 for n = 10-22, Compounds of
composition C27H4402, C27H440, C27H420 , C28H46 O, C28H440 , C29H48, C27H44 ,
C27H46 , C27H48, etc. are present in significant amounts and are probably steroidal in
nature. These functionalized homologs cannot be analyzed underivatized by GC but are
easily detected by HRMS. The presence of phthalate esters is indicated by the peak of
composition CsHsO 3 (m/e 149). Carboxylic acids or acid esters are not detectable from
these data.
The outward similarity of the GC trace of the site 17 sample to that of fuel oil
(Boylan and Tripp 1971) is misleading. Coinjection of naphthalene and methyl
naphthalene with the site sample did not yield enhancement of the appropriate peaks.
Furthermore, if the major GC peaks tbr the site 17 extract were naphthalenes, it is
expected that the HRMS data of Figure 5 would show evidence of intense ions (which
in fact is not the case).
Another interesting example of compounds which do not pass through a GC column
is found in the extract from the sample taken at site 16. The C/H 02 data (Fig. 5)
exhibit strong peaks of compositions C 4 oH6602 and C4 oH64 02. It is possible that these
compounds are partially reduced oxygenated C4o carotenoids which are well known
components of phytoplankton or wax esters (Lee et al. 1971). The source of these com-
pounds is at present unknown.

Conclusions
The described total-mixture analysis is sensitive and small amounts of material
yield a substantial data return. With such small samples, the major components can
be picked out and some types identified. This approach points the way to additional,
more detailed experiments and more extensive sample grid correlations. A single high-
resolution mass spectrum is an invaluable aid in searching for specific organic com-
pounds indicative of particular metabolic or diagenetic processes (e.g., steroidal com-
pounds in the extract of sample 17) which can subsequently be analyzed in more detail.
However, from these preliminary" data reported here, no obvious correlations with visi-
ble water quality (e.g., algal concentration or turbidity) are possible. The relatively
low amounts of dissolved organic matter in the water samples indicate that the "'mud
oozes" of the surface sediments possibly are more organic carbon rich and play' a greater
role than water, in organic carbon transport (Hood 1970). It is possible that more work
will develop intercorrelations with analogous sediment programs, such as the Deep Sea
Drilling Project cores (Simoneit and Burlingame 1972), Black Sea cores (Simoneit 1973b),
and San Francisco Bay Area sediment samples (under study in these laboratories).
The sample taken in the vicinity of a domestic waste discharge area (site 5) exhibits
a hydrocarbon distribution attributable to biotic activity (i.e., the strong
odd-over-even alkane distribution pattern found in higher plants, microbes, and algae).
The other estuarine- and bay samples (sites 3, 4, 7 - 14, and 16) exhibit generally
similar alkane distributions with the same predominance and usually a maximum
at C25. The source of the lanostane (sites 13 and 14) is unknown. The samples taken
206 B.R. Simoneit et al.

at oil refinery docks (sites 15 and 17) exhibit complex hydrocarbon mixtures with signif-
icant amounts of more volatile alkanes below C2o. The site 15 extract exhibits a typical
gasoline residue GC pattern.

Pesticide residues, especially potychlorinated hydrocarbons, were not detected in our

data. Polychlorinated biphenyls (PCB s) were found in California coastal waters, mainly
near sewage outflows (Schmidt et al. 1971), when using electron capture GC analysis, a
technique highly sensitive to halogenated compounds. The absence of halogenated ions in
the data given in this paper indicates that organic matter, other than pesticide or PCB
residues, is the predominant organic residue in the water of the San Francisco Bay Area.

Several of the extracts examined in the present study show significant amounts of
phthalate esters. In view of the recent concern over phthalate contamination in blood
serum samples (Jaeger and Rubin 1970) and other sources (Simoneit and Flory 1971,
Simoneit 1973a), it is important to point out that the above-mentioned MS techniques
are particularly sensitive to phthalates. The data given in this paper further serve to
indicate the contamination of the environment by phthatates.

The possible deleterious effects on biota of various mixtures of organic compounds,

such as those mentioned here, have received little attention, to date. The HRMS
technique is ideally suited to assess some of these potential interactions of such mixtures
in the water environment.

Acknowledgments

The authors thank Mrs. A. Sadorra for technical assistance, Dr. J. Chang and Mrs.
E. Scott for GC/MS analyses, Miss R. Jackson for high-resolution mass spectral data
acquisition, Mr. C. Wong for data reduction, and Mr. T. Tighe for kindly providing
the sampling craft. Financial support from the National Aeronautics and Space Adminis-
tration (NASA Grant NGL 05-003-003) is gratefully acknowledged.

References

Boytan, D. B.: Private communication (1971).

Boylan, D.B., and B. W. Tripp: Determination of hydrocarbons in sea water extracts
of crude oil and crude oil fractions. Nature 230, 44 (1971).
Burlingame, A. L.: Data acquisition, processing and interpretation via coupled high-
speed real-time digital computer and high-resolution mass spectrometer systems.
In Kendrick, E. (ed.): Advances in mass spectrometry, vol. 4, p. 15. London:
The Institute of Petroleum (1968).
 Mass Spectrometric Identification of Organic Matter in S. F. Bay Water 207

Burtingame, A.L., and D. H. Smith: Automated heteroatomic plotting as an aid to

the presentation and interpretation of high-resolution mass spectral data. Tetrahed-
ron 24, 5749 (1968).
Burlingame, A. L. : Developments and applications of real-time high-resolution mass
spectrometry. In Ogata, K. and T. Hayakawa (eds.): Recent developments in mass
spectrometry, p. 104. Tokyo: University of Tokyo Press (1970).
Burlingame, A. L., D. H. Smith, T. O. Merren, and R. W. Olsen: Real-time high-
resolution mass spectrometry. In Orr, C. H. and J. Norris (eds.): Computers in
analytical chemistry, vol. 4 of Progress in Analytical Chemistry Series, p. 17.
New York: Plenum Press (1970).
Chang, J. J., F. C. Walls, D. H. Smith, B.R. Simoneit, and A. L. Burlingame: The
LOGOS classifier--a compound classifier based on computer analysis of mass
spectrometric data. In preparation (I973).
Ciaccio, L. L., (ed.): Water and water pollution handbook. See especially Painter, H.
A.: Chemical, physical and biological characteristics of wastes and waste effluents,
vol. I, chapter 7. New York: M. Dekker (1971).
Eglinton, G., and M. T. J. Murphy (eds.): Organic geochemistry methods and results.
Heidelberg: Springer-Verlag (1969).
Garrison, A. W., L. H. Keith, and M. M. Walker: The use of mass spectrometry in
the identification of organic contaminants in water from the Kraft paper mill
industry. In: Proc. 18th annual conference on mass spectrometry and allied topics,
p. B205. San Francisco, California, June 1970.
Hites. R. A., and K. Biemann: Computer evaluation of continuously scanned mass
spectra of gas chromatographic effluents. Anal. Chem. 42, 855 (1970).
Hood, D. W. (ed.): Symposium on organic matter in natural waters. UniversiO' of
Alaska: Institute of Marine Science (1970).
Jaeger, R.J., and R. J. Rubin: Plasticizers from plastic devices: Extraction, metabolism,
and accumulation by biological systems. Science 170, 460 (1970).
Lee, R. F., J. C. Nevenzel, and G. A. Paffenh6fer: Importance of wax esters and other
lipids in the marine food chain: phytoplankton and copepods. Marine Biology 9,
99 (1971).
Scher, J. A.: Measurement of trace organic pollutants in aqueous solutions. Amer. Lab.
2, 24 (1970).
Schmidt, T. T., R. W. Risebrough, and F. Gross: Input of polychlorinated biphenyls
into California coastal waters from urban sewage outfalls. Bull. Environ. Contain.
Toxicol. 6, 235 (1971).
Simoneit, B . R . , a n d D. A. Flory: Apollo 11, 12 and 13 Organic Contamination
Monitoring History. NASA Division Internal Note, MSC 04350, NASA-Manned
Spacecrc~'t Center, Houston (May 1971).
Simoneit, B. R.: Apollo 14 organic contamination monitoring history. University of
California Space Sciences Laboratory Report, in press (1973a).
208 B. R, Simoneit et al.

Simoneit, B. R.: Organic analyses of Black Sea cores. In Degens, E.T. and D.A.
Ross (eds.): The Black Sea: geology, chemistry and biology, in the Memoir Series
of the American Association of Petroleum Geologists, in press 1973b).
Simoneit, B. R,, and A. L. Burlingame: Preliminary organic analyses of the DSDP
(JOIDES) cores, legs V-IX, In yon Gaertner, H, and H. Wehner (eds.): Advances
in organic geochemistry 1971, p. 189. Oxford-Braunschweig: Pergamon Press
(1972).
Simoneit, B. R., D. H. Smith, G. Eglinton, and A. L. Burlingame: Applications of
real-time mass spectrometric techniques to environmental organic geochemistry.
I. General considerations. In preparation (1973).
Smith, D. H., R. W. Otsen, F. C. Walls, and A. L. Burlingame: Real-time mass
spectrometry: LOGOS--a generalized mass spectrometry computer system for high
and low resolution, gas chromatography/mass spectrometry, and closed-loop appli-
cations. Anal. Chem. 43, 1796 (t97I).
Smith, D. H.: A compound classifier based on computer analysis of low-resolution
mass spectral data. Geochemical and environmental applications. Anal. Chem. 44,
536 (1972).
Taras, M. J., A. E. Greenberg, R. D. Hoak, and M. C. Rand (eds.): Standard methods
for the examination of water and waste-water, 13 ed., pp. 254-256. New York:
American Public Health Assoc, (1971).

Manuscript received October 3, 1972; accepted October 20, 1972