Marine Pollution Bulletin 96 (2015) 29–31

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Marine Pollution Bulletin

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Viewpoint

‘‘Unresolved Complex Mixture’’ (UCM): A brief history of the term

and moving beyond it
John W. Farrington a,⇑, James G. Quinn b
a
MS#8, Woods Hole Oceanographic Institution, Woods Hole, MA 02543, USA
b
Graduate School of Oceanography, University of Rhode Island, 215 South Ferry Road, Narragansett, RI 02882-1197, USA

a r t i c l e i n f o a b s t r a c t

Article history: The term ‘‘Unresolved Complex Mixture’’ (UCM) has been used extensively for decades to describe a gas
Received 6 March 2015 chromatographic characteristic indicative of the presence of fossil fuel hydrocarbons (mainly petroleum
Revised 17 April 2015 hydrocarbons) in hydrocarbons isolated from aquatic samples. We chronicle the origin of the term. While
Accepted 18 April 2015
it is still a useful characteristic for screening samples, more modern higher resolution two dimensional
Available online 29 April 2015
gas chromatography and gas chromatography coupled with advanced mass spectrometry techniques
(Time-of-Flight or Fourier Transform-Ion Cyclotron Resonance) should be employed for analyses of pet-
Keywords:
roleum contaminated samples. This will facilitate advances in understanding of the origins, fates and
Unresolved Complex Mixture
UCM
effects of petroleum compounds in aquatic environments.
Oil pollution Ó 2015 Elsevier Ltd. All rights reserved.

Advances in application of parallel chromatographic methods
and three different types of mass spectrometry (MS) (e.g. Gough
and Rowland, 1990) and multidimensional gas chromatography
(GC) (e.g. Frysinger et al., 2003) or two-dimensional GC coupled
with time of flight MS (e.g. Booth et al., 2007) have at least partially
resolved or essentially completely resolved the Unresolved
Complex Mixture of hydrocarbons in petroleum samples and in
several environmental samples from petroleum contaminated or
oil spill contaminated and polluted environments. The extent of
the partial or essentially complete resolution depends on molecu-
lar weight range and molecular type of compounds present, e.g. No.
2 fuel oils are essentially completely resolved, and some crude oils
are partially resolved. These advances have stimulated another
round of inquiries similar to those we have been asked numerous
times during the past forty years about the origin of the term
‘‘Unresolved Complex Mixture’’ or UCM, a term still in use as one
indicator of petroleum or fossil fuel pollution (e.g. Wang et al.,
2015). To our knowledge and extensive literature research, the
term, including the shorthand notation UCM, was first used in
our paper Farrington and Quinn (1973a). At that time, we had no
inkling of how extensively it would be used. We provide here a
short account of the history of the term which has been used in
hundreds, if not thousands, of scientific papers, chapters and tech-
nical reports since 1973, including numerous papers published in
Marine Pollution Bulletin.
⇑ Corresponding author. Tel.: +1 508 274 1926.
E-mail addresses: jfarrington@whoi.edu (J.W. Farrington), jgquinn@uri.edu (J.G.
Quinn).
One of us (JWF) was a Ph.D. student advised by the other (JGQ) at
the Graduate School of Oceanography, University of Rhode Island
1968–1971. JWF’s Ph. D. Dissertation research initially focused in
part on the use of lipid class compounds in sewage discharges to
Narragansett Bay, R.I. USA as a potential means of tracking sewage
inputs to the bay. One of the target classes of compounds selected
for testing was the class n-alkanes. We knew from earlier research
that n-alkanes with an odd over even carbon number predominance
in the molecular weight range of 23–31 carbons chain length were
predominant in land plants as constituents of the waxy coating on
plants (Eglinton et al., 1962a,b). Marine organisms did not have
such an n-alkane distribution, with odd over even carbon number
predominance in a limited range of 22–31 carbon chain length.
(Clark and Blumer 1967, among others).
We set out sampling sewage discharge waters from a large
municipal sewage treatment plant, surface sediments in
Narragansett Bay and hard shell clams (Mercenaria mercenaria),
extracting the lipid class compounds, and isolating several classes
of lipids by column chromatography (CC), thin layer chromatogra-
phy (TLC), and analyzing the hydrocarbon fraction by gas chro-
matography using a packed column in a temperature
programmed gas chromatograph (GC) equipped with a flame ion-
ization detector connected to a strip chart recorder.
These were our first hydrocarbon analyses and we expected to
see a series of resolved n-alkanes, pristane and phytane peaks as
had been reported in the literature for sediments and marine
organisms and which we had replicated with standard mixtures
of n-alkanes. Instead we had a slowly rising slightly wiggling graph
trace over time, with a few small peaks on top of this line that

http://dx.doi.org/10.1016/j.marpolbul.2015.04.039
0025-326X/Ó 2015 Elsevier Ltd. All rights reserved.
30 J.W. Farrington, J.G. Quinn / Marine Pollution Bulletin 96 (2015) 29–31

gradually came back to the column bleed background of the GC
column as the temperature program run ended (Fig. 1). We
thought that JWF had done something wrong. Several extractions,
isolations by CC, TLC, and GC analyses were repeated. Nothing
changed and we were perplexed. The gas chromatograms were
placed on a shelf, the TLC isolates were stored in vials in a refriger-
ator, and JWF got on with the fatty acid analyses which were also
part of his dissertation research.
A few months later a clue to what we were measuring in the gas
chromatograms of the hydrocarbons was discovered in an ongoing
literature search. JGQ required all his students to participate in a
coordinated lab group literature search on topics of interest to
our group, e.g. lipids, hydrocarbons, fatty acids, triacylglycerols.
As part of this, JWF was searching Chemical Abstracts when he
came across an abstract of a paper ‘‘Microbiological Alterations of
Crude oil in the Reservoir’’ by J.C. Winters and J.A. Williams pre-
sented at a Symposium on Petroleum Transformations in
Geological Environments of the Division of Petroleum Chemistry,
Inc. of the American Chemical Society Meeting, September 7–12,
1969. The abstract in Chemical Abstracts was intriguing. That divi-
sion of the ACS had published extended abstracts from the ACS
meetings and we requested one from the authors by mailing a rep-
rint request card, a common practice in those days. The extended
abstract arrived within a few weeks. It contained figures with
reproductions of the packed column gas chromatograms of the
unaltered reservoir crude oil of the Bell Creek Formation on the
border of Montana and Wyoming, and gas chromatograms of a
transect of samples from the near surface reservoir of that forma-
tion which received a groundwater incursion with nutrients and
oxygen. The former contained many resolved peaks of n-alkanes
and branched alkanes superimposed on a broad rising and falling
background signal. For the latter, the n-alkane peaks were much
reduced or missing for the transect samples and isoprenoid alkanes
were predominant and superimposed on the rising and falling
broad background signal. The broad, non-descript rising and then
and falling gas chromatogram signal was attributed by inference
to a naphthenic (mainly cycloalkanes) character to the biode-
graded crude oil (Winters and Williams, 1969)
It was an ‘‘aha’’ moment for us. Immediately we reasoned that
our gas chromatograms of alkane hydrocarbons isolated from sew-
age effluents, surface sediments and hard shell clams were of
biodegraded oil and/or lubricating oil (known to be mainly naph-
thenic in composition) being discharged via the sewage effluent
(and perhaps other sources) to Upper Narragansett Bay. In hind-
sight, one could argue we should have expected chronic oil
released via sewage effluents. However, our literature search in
1968 and 1969 had yielded many papers about measurements of
total ‘‘grease and oil’’ – meaning animal fats and vegetable oils
mainly from household and restaurant sources, and some specific
analyses of fatty acids.
Shortly thereafter, in 1970 a paper was published reporting the
presence of No. 2 fuel oil components in edible shellfish as result of
the Barge Florida No. 2 Fuel Oil spill on September 16, 1969 at the
coast of West Falmouth in Buzzards Bay, Massachusetts, USA
(Blumer et al., 1970). The gas chromatograms again contained
the series of resolved or partially resolved peaks on top of the
broad rising and falling detector signal. In that publication,
Blumer et al. designated the phenomenon as the unresolved back-
ground. Blumer et al. (1970, 1973) and Blumer and Sass (1972)
designated this signal the unresolved envelope of oil compounds.
The term unresolved envelope seemed like a good term to us and
JWF used it in his Ph. D. dissertation to describe attributes of our
hydrocarbon gas chromatograms from several samples of sewage
effluents, surface sediment samples, and hard shell clams obtained
in Narragansett Bay.
JWF took a position as a Postdoctoral Investigator in Max
Blumer’s laboratory at Woods Hole Oceanographic Institution in
July 1971. Throughout the remainder of 1971 and into 1972 JWF
presented seminars and talks at various places and meetings dur-
ing which he presented slides with the term ‘‘unresolved envelope’’
while preparing papers from his dissertation for publication. One
paper (Farrington and Quinn, 1973b) was prepared, submitted,

Fig. 1. Packed column gas chromatograms of hydrocarbons isolated from Narragansett Bay surface sediments (left column) and Mercenaria mercenaria (right column). N–C22–
alkane added as internal standard in the right column chromatograms. Stations F.P. and E. were in the Providence River area of Upper Narragansett Bay that received
municipal and storm sewer discharges from municipal Providence R.I., Stations D and C were in the mid to upper reaches of Narragansett Bay. Charlestown Pond is a rural
area and the control for the study. The chromatogram trace for the Charlestown Pond sample is the same as for the laboratory control and indicates the GC baseline for the
temperature controlled GC analysis. (Figure reproduced with permission from Farrington and Quinn (1973a)).
 J.W. Farrington, J.G. Quinn / Marine Pollution Bulletin 96 (2015) 29–31
and accepted for publication in which we used the term unresolved
envelope as used by Blumer et al. (1970, 1973) and Blumer and
Sass (1972). During JWF’ seminars and talks, the term ‘‘unresolved
envelope’’ was criticized by some analytical chemists as not wor-
thy of mention because we ‘‘had failed to resolve the compounds
yielding the signal’’. We understood that concern, but thought that
the signal should not be ignored and we believed we were in good
company in that regard. Other critics did not like the term ‘‘en-
velope’’. Some remarked during a few seminars that an ‘‘envelope
was something in which one mailed a letter’’. These criticisms led
JWF to suggest that we use the term ‘‘Unresolved Complex
Mixture’’, which would acknowledge we had not resolved the com-
ponents of this complex mixture, and use the words ‘‘complex mix-
ture’’ as noting the presence of the complexity of hydrocarbons
found in fossil fuels such as crude oil and fuels and coal extracts.
In reproductions of the gas chromatograms we used the short hand
UCM to label the Unresolved Complex Mixture when it was present
(Farrington and Quinn, 1973a). Fig. 1.
Our only caveat that this might not be petroleum hydrocarbons
was a concern that perhaps hydrocarbons biosynthesized by a very
complex assemblage of microbes in sewage might yield the UCM
signal. Discussion with Oliver C. Zafiriou, also in Max Blumer’s lab-
oratory at that time, about that possibility led to additional analy-
ses of hydrocarbons from a large several kg sediment sample from
Upper Narragansett Bay/Providence River and a companion paper
to our 1973a paper (Zafiriou, 1973). He reported radiocarbon
(D14C) activity for hydrocarbons extracted and isolated from the
sample of sediment indicating that the carbon in hydrocarbons of
the UCM were 80–97% fossil, consistent with a fossil fuel source.
This type of measurement for the radiocarbon (D14C) activity of
hydrocarbons extracted from surface sediments was repeated a
few years later for a sediment sample from the New York Bight
Sewage Sludge Dump site (Farrington and Tripp, 1977) and more
recently for samples of coastal sediments, road dust and urban
atmospheric particulate samples with the result that 90% or
greater of the carbon of the UCM was fossil carbon and therefore
arguably from fossil fuel contamination/pollution (White et al.,
2013).
Professor Kurt Grob, a pioneer in analytical chemistry especially
using glass capillary gas chromatography, took up a challenge from
Dr. Max Blumer during the period 1973–74 and proceeded to
almost completely resolve all the hydrocarbon components in a
diesel oil (similar in molecular weight range to No. 2 Fuel Oil) into
individual GC peaks using ingenious but time consuming glass cap-
illary chromatography with 70 m columns, 3 h temperature pro-
grammed techniques, and transfer of several minute time
portions of the first capillary GC column to a second glass capillary
column for further separation (Grob, 1975). His methods were the
forerunners of modern two dimensional GC analyses.
Unfortunately, the time consuming nature of the methodology,
about three or usually more hours per GC analysis, and the difficult
art of preparing the fragile glass capillary columns, precluded rou-
tine analyses of oil contaminated samples by this methodology for
several years.
Identification and quantitative analyses of the major polycyclic
aromatic hydrocarbons (PAH) from fossil fuels and pyrogenic
sources in the aromatic hydrocarbon fraction of extracts of envi-
ronmental samples proceeded in the interim years via probe distil-
lation MS and GS–MS (e.g. Youngblood and Blumer, 1975; Hites
and Biemann, 1975). Despite these advances, there are many aro-
matic hydrocarbons in the aromatic fraction UCM which were
not identified and quantified. A very important study by Booth
et al. (2007) found that several of the compounds contributing to
the aromatic hydrocarbon UCM are toxic. Booth et al. noted that
the potential for adverse effects from the UCM aromatic com-
pounds had been overlooked.
31
The UCM signal may continue to be a screening tool for identi-
fying samples containing complex mixtures of hydrocarbons in
samples to become candidates for further analyses. However,
when complex mixtures are identified, we call for the routine
application of more modern analytical techniques such as multi-
dimensional GC capable of resolving the components of the UCM,
coupled with various types of mass spectrometry to identify these
components and quantify concentrations (e.g. Gros et al., 2014).
Simultaneously, it is important to gain a better understanding of
the relationship between the identified compounds and mixtures
of compounds, bioaccumulation potential and biological effects
as pointed out by Booth et al. (2007).
Acknowledgements
John W. Farrington conceived of the idea of this Viewpoint arti-
cle and led the writing. James G. Quinn added substantive com-
ments and suggestions. Both authors approve submission of the
manuscript. The authors have no substantive conflicts of interest
that pertain to this article to disclose. This manuscript was self-
funded. Both authors are formally retired.
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