Artículo en PDF
How to cite
Complete issue
More information about this article
Journal's homepage in redalyc.org
Sistema de Información Científica
Red de Revistas Científicas de América Latina y el Caribe, España y Portugal
PETROLEUM HYDROCARBON ASSESSMENT IN THE SEDIMENTS OF THE
NORTHEASTERN HAVANA LITTORAL, CUBA
Eloy Yordad COMPANIONI DAMAS
1
, Ana Catalina NÚÑEZ CLEMENTE
1
,
Miriam Odette CORA MEDINA
1
, Luís GONZÁLEZ BRAVO
2
, Rolando MARBOT RAMADA
3
,
Rodny MONTES DE OCA PORTO
4
, Maikel ROSABAL RODRÍGUEZ
5
and Miguel Ángel DÍAZ DÍAZ
1
1
Laboratorio de Química Ambiental, Centro de Investigaciones del Petróleo, 169 Calle Washington # 169,
Cerro, Habana, Cuba. Email: elocompa@yahoo.com
2
Centro de Aplicaciones Tecnológicas y Desarrollo Nuclear, 30 Aven., Playa, Habana, Cuba.
3
Laboratorio de Química Analítica, Centro de Investigaciones del Petróleo, 169 Calle Washington # 169, Cerro,
Habana, Cuba.
4
Laboratorio Antidoping, Calle 100, Altahabana, Habana, Cuba.
5
Centro de Ingeniería y Manejo Ambiental de Bahías y Costas, Casablanca, Habana, Cuba.
(Recibido enero 2008, aceptado agosto 2008)
Keywords: petroleum hydrocarbons, coastal sediments, Havana, Cuba
ABSTRACT
As a part of a geochemical study, aliphatic and aromatic hydrocarbons were determined
in surfcial sediments, From a Cuban coastal zone located in the Northeastern Havana
Littoral. Sediment samples were collected at 15 sites in this area, and then extracted
and analyzed by gas chromatography with ±ame ionization and mass spectrometry
detectors. Total concentration of both, aliphatic (AH) and aromatic (ArH) hydrocar-
bons, varied from 2.4
±
0.2 to 105.1
±
5.9
µ
g/g (dry weight) and from 1.1 ± 0.2 to
38.4 ² 7.6 µg/g (dry weight), respectively. The chromatography profle oF AH was
dominated by an unresolved complex mixture (UCM), and the presence of isoprenoid
hydrocarbons, steranes and hopanes, indicated petroleum - related hydrocarbon in-
puts. The predominant concentration of phytoplanktonic molecular markers (pristane
and nC
17
) in collected sediments, revealed the marine productivity in this sites. The
anthropogenic contribution detected showed the impact of the petroleum exploration
along this coastal area.
Palabras clave: hidrocarburos del petróleo, sedimentos costeros, Habana, Cuba
RESUMEN
Como parte de un estudio geoquímico se determinaron hidrocarburos alifáticos y aromá-
ticos en sedimentos superfciales, de una zona costera situada en el Litoral Nordeste de
La Habana.
Las muestras de sedimento se colectaron en 15 estaciones
de muestreo en
esta área, y posteriormente se extrajeron y analizaron mediante cromatograFía gaseosa
con detectores de ionización a la llama y espectrometría de masas. Las concentraciones
totales de hidrocarburos alifáticos (HA) e hidrocarburos aromáticos (HAr) variaron
desde 2.4
±
0.2 a 105.1
±
5.9
µ
g/g (peso eco) y desde 1.1 ± 0.2 a 38.4 ± 7.6 µg/g (peso
eco), respectivamente. El perfl cromatográfco de los hidrocarburos aliFáticos estuvo
Rev. Int. Contam. Ambient. 25 (1) 5-14, 2009
E.Y. Companioni Damas
et al.
6
dominado por una mezcla compleja no resuelta (MCNR), y la presencia de hidrocar
-
buros isoprenoides, esteranos y hopanos, indicó el aporte de hidrocarburos derivados
del petróleo. La concentración predominante de marcadores moleculares ftoplanctó
-
nicos (pristano y ftano) en los sedimentos colectados, reveló la productividad marina
en estos sitios. La contribución antrópica detectada demostró el impacto que ejerce la
exploración petrolera a lo largo de esta área costera.
INTRODUCTION
Research on coastal environments has been rec-
ognized as critical For achieving a sustainable man
-
agement and ecosystem preservation. Pollutants are
often introduced in off shore areas by land-production
activities and have signifcant impact on coastal eco
-
system and public health. Petroleum hydrocarbons
constitute one of the more frequently detected pol-
lutants in marine ecosystems (Hostettler
et al.
1999,
Eganhouse
et al.
2000, Burns
et al.
2001, Dojiri
et al.
2003, Wu
et al.
2003, Ahrens
et al.
2004). Extensive
transportation of petroleum by ocean going tankers
and oil exploration in coastal areas, make marine
and coastal environments particularly vulnerable to
pollution.
When crude oil enters the surface environment, it
is immediately subject to a number of processes that
are collective known as weathering (Wang
et al.
1995).
Some hydrocarbon compounds evaporate, some dis-
solve, some are dispersed, some are photooxided, some
absorb onto suspended particulate materials, and the
majority are eventually biodegraded.
Aside from anthropogenic sources, hydrocarbons
have also several natural ones such as terrestrial plant
waxes, marine phytoplankton and bacteria, biomass
combustion, and diagenetic transformation of bio-
genic precursors (Parrish
et al.
2000, Faure
et al.
2000, Medeiros
et al.
2004). As a result of the variety
of their sources hydrocarbons occur as complex mix-
tures in environmental samples. The differentiation of
hydrocarbons with anthropogenic origin from those
which are derived from natural sources, or by natural
processes, is quite necessary for the assessment of
accumulation and biodegradation of these compouns
in marine environment.
In aliphatic fraction many sources for hydrocar-
bons are possible, including oil pollution and natural
petrogenic inputs from oil seeps and from the erosion
of ancient rocks (Peters
et al.
2005). The presence
of hopanes, steranes, an unresolved hump, and the
lack of odd /even carbon-number predominance of
n-alkanes may indicate pollution (Wang
et al.
2003).
There are also biogenic alkanes and alkenes which
are relatively specifc to the biota which produces
them. Planktonic and benthic organisms synthesize
hydrocarbons clearly distinguishable from the hydro-
carbons found in the surface waxes of higher plants
(Zegouagh
et al.
1998, Gomes
et al.
2003).
Coastal ecosystem located in Northeastern Ha-
vana Littoral, among Bacunayagua inlet (23
o
08’31”
N - 81
o
40’34” W) and Guanabo strand (23
o
10’19”
N - 82
o
05’50” W), is one of the most important areas
of Cuba used for oil exploration. This area receive
domestic untreated wastes from several riverine
discharges, however this has not become a drastic
environmental quality problem. On the contrary, the
oil extraction wells and pipelines located along this
coast, has caused the input of petrogenic pollutants
towards this marine environment. Previous studies
(Nuñez 2002) reported total hydrocarbon concentra
-
tion in sediments of 5.3 to 300
µ
g/g. Nevertheless,
almost nothing is known in relation to the organic
geochemistry oF surFace sediments oF this zone. In
this respect, the present paper focuses on the determi-
nation of composition, levels and sources of hydro-
carbons in sediments of this area. The assessment of
the various biogenic and anthropogenic sources was
achieved by using molecular marker approach, char-
acteristic compositional patterns and related indices
(Simoneit
et al.
1982, Simoneit 1984).
MATERIALS AND METHODS
Sampling
In order to evaluate hydrocarbon inputs from natu-
ral and anthropogenic sources to the Northeastern Ha-
vana Littoral, 15 sediments samples were collected in
March 2006 at the sites shown in
fgure 1
. Sediments
were collected utilizing a Van-Veen grab. Only the top
5 cm of undisturbed surface sediment were sampled.
±ive replicated grabs were taken and homogenized
in a bucket to provide a single composite sample for
each station. Homogenized samples were placed in
pre-cleaned aluminium boxes, and then stored in a
Freezer at
-
20
o
C until laboratory analysis. Before
extraction, sediments were defrosted, dried (45
o
C)
overnight and passed through a sieve (2000 µm) to
PETROLEUM HYDROCARBONS ASSESSMENT IN SEDIMENTS OF NORTHEASTERN HAVANA LITTORAL
7
remove gravel and detritus.
Extraction and fractionation
About 30 g of homogenized dry sediment were
Soxhlet-extracted with 150 ml of dichloromethane
for a period of 16 h. Activated powder copper (5 g)
was added to the extraction balloons for elemental
sulphur removal. The extract was dried in a col-
umn containing glass wool and 2 g of Na
2
SO
4
, and
concentrated on a Kuderna Danish to a volume of
approximately 2 ml. The extraction solvent was
exchange to ciclohexane and the further volume
reduction was achieved with a gentle stream of ultra
pure nitrogen until 0.5 ml. The cleanup procedure
used a column Flled with 7 g of alumina (35 - 70
mesh, Merck) (top) and 7 g of silica (35 - 70 mesh,
Merck) (bottom). Both adsorbents were previously
activated at 240
o
C for 4 h, afterwards 2 % and 5 %
by weight of milli-Q water were added to alumina
and silica, respectively, to obtain consistent activa-
tion. 0.5 g Na
2
SO
4
was added to the top for removing
trace amounts of water. Afterwards the extract was
adsorbed on to the top of the column. The aliphatic
fraction was recovered by elution with hexane (20
ml), and the aromatic fraction with 1:1 (v/v) hexane/
dichloromethane mixture (20 ml).The eluates were
concentrated with nitrogen until the required volume
for analysis by GC/FID and GC/MS.
Instrumental analyses
Aliphatic and aromatic hydrocarbon analyses
were conducted on a Konik HR 4000B gas chro-
matograph with ±ame ionization detector (GC/²ID).
The samples were analyzed using a DB-1 fused silica
capillary column (30 m, 0.25 mm i.d., 0.25 µm Flm
thickness, Tecknocroma, Spain) with hydrogen as
carrier gas. The injector and detector were held at 300
o
C. The column temperature program for aliphatic
fraction analysis was 60
o
C (2 min), followed by
heating to 300
o
C at 6
o
C/min (isothermal hold for
20 min), and for aromatic fraction analysis was 80
o
C (5 min), followed by heating to 300
o
C at 6
o
C/
min (isothermal hold for 20 min).
Selected fractions were analyzed by gas chro
-
matography-mass spectrometry (GC/MS) using a
Hewlett Packard 6890 equipped with a 5973 MSD.
The capillary column used was coated with DB-1 (12
m, 0.20 mm i.d., 0.33 µm Flm thickness, HP Ultra
II, USA) with helium as carrier gas. The injector and
detector were held at 280
o
C and 300
o
C, respectively.
The ionization was carried out in the electron impact
mode (70 eV). The electron multiplier voltage and
automatic gain control target were set at 290
o
C and
230
o
C, respectively. The MS operated in a total ion
current (TIC) mode, and the mass range scanned was
from 50 to 550 amu. The column was held at 60
o
C
for 2 min, increased to 290
o
C at a rate of 3
o
C/min,
and held for 10 min.
Compound identiFcation was based on individual
mass spectra and GC retention times in comparison to
library data and authentic standards.
Standards were
injected and analyzed under the same conditions as
the samples. GC/FID provides a baseline resolution
of n-alkanes from nC
14
to nC
35
and nC
17
/pristane and
nC
18
/phytane. Separate external standard calibration
curves were established for the quantiFcation of each
n-alkane and PAH. QuantiFcation of unresolved
complex mixture (UCM) of hydrocarbons was per-
formed using collective calibration curves formed
by standard mixtures.
Quality assurance
In order to achieve the improved analytical preci-
sion and the accuracy, a number of measures were
added to the processing of samples to monitor quality
control. Spiked sediment samples with increasing
concentration over a range between 33 and 200 ng/g
were analyzed. The limit of detection (LOD) and the
limit of quantiFcation (LOQ) were determined as the
concentration of analyte in a sample that produce a
signal-noise ratio (S/N) of 3 and 10, respectively.
The uncertainty of quantitative results was estimated
using the recovery results according to Barwick and
Ellison (1999, 2000). For every bath of 20 sediment
samples, a procedure blank was run to check for
interference and cross contamination.
RESULTS AND DISCUSSION
Table I
illustrates the extraction recoveries and
the relative standard deviations (RSD, %) obtained
HAVANA
ATLANTIC OCEAN
Guanabo
River
0
2.5
5
Km
10
15
14
15
13
N
W
S
E
12
11
10
9
8
7
6
5
4
3
2
1
Jaruco
River
Jibacoa
River
Canasi
River
Bacunayagua
River
Fig. 1.
Location of the sampling area in the Northeastern Havana
Littoral
E.Y. Companioni Damas
et al.
8
for the spiked levels of 66 and 116 ng/g. LOD and
LOQ are also showed. The recoveries of n-alkanes
and polycyclic aromatic hydrocarbons (PAH) ranged
from 49.1 to 105.6 %. Only the more volatile analytes
show recoveries below 40 %. PAH show RSD values
slightly higher than n-alkanes. Similar extraction ef-
fciency and precision were achieved by other authors
at comparable concentration levels (Jaoen-Madoulet
et al.
2000). LOD and LOQ values ranged from 19.26
to 35.97 ng/g and 29.40 to 65.75 ng/g, respectively for
n-alkanes, and from 16.74 to 45.87 ng/g and 29.98 to
82.82 ng/g, respectively for PAH.
Table II
gives the total concentrations of the
aliphatic hydrocarbons and n-alkanes ranging from
nC
14
to nC
32
, as well as diagnostic criterias useful for
the identifcation oF natural and anthropogenic origins
of hydrocarbons. The total aliphatic hydrocarbon
concentrations varied from 2.4
±
0.2 to 105.1
±
5.9
µ
g/g (dry weight). Higher concentration occurred
at sites 10 - 13. These sites are located in an area of
intensive oil exploration. Lower concentrations were
found for samples 6 and 7. These samples were col-
lected at strands situated far-away from petroleum
extraction installations.
The total n-alkane concentrations ranged from
0.10
±
0.06 to 2.37
±
0.19
µ
g/g (dry weight). Higher
concentrations were found at sites 1, 9, 12 and 13, and
lower concentrations at sites 6 and 7. Total n-alkanes
found in the samples represented only a minor amount
of the total aliphatic hydrocarbons. The majority of
the compounds present in this fraction are molecules
that can not be resolved by capillary GC columns
and are termed unresolved complex mixture (UCM).
The UCM appears in the GC trace as a hump area
between the solvent baseline and the curve defning
the base of resolvable peaks
(
Fig. 2
). It consists of a
complex mixture of branched alicyclic hydrocarbons
(Peters
et al.
2005), and has a well-known linkage to
biodegraded petroleum residues (Wang and Fingas
1995, Wang
et al.
1998 a,b, Grossi
et al.
2002). The
UCM shape depends on the hydrocarbon composition
in these samples.
Figure 2
shows chromatograms
with bimodal envelopes in the elution ranges between
nC
17
- nC
25
and nC
25
- nC
34
.
The high abundance of UCM in all sampling sites
(2.3
±
0.2 - 102.7
±
5.8
µ
g/g (dry weight);
Table II
),
is a positive indication of chronic oil - pollution. Ad-
ditional evidence is provided by the ratio of UCM to
NA (UCM/NA) which at all sampling sites take values
>
5 up to 61.8. This range characterizes hydrocarbon
mixtures with signifcant contribution From degraded
petroleum products (Simoneit and Mazuret 1982,
Simoneit 1984). Higher UCM values which corre-
spond to sites 10 - 13, indicates that more signifcant
petroleum-related inputs occurred at this zone.
In the GC-chromatogram of aliphatic hydrocar-
bons (
Fig. 2
), the most prominent resolved compo-
nents are represented by the homologous series of
n-alkanes ranging in carbon number from nC
14
to
nC
34
. These compounds are shown more clearly in
the m/z 85 Fragmentograms (
Fig. 3
) which allowed
the characterization oF n-alkanes and isoprenoid
hydrocarbons, with less interference of the UCM
constituents. In the case of weathered hydrocarbons,
the chromatograph profles usually appears with a
very different GC trace, in which the n-alkanes are
almost completely lost, and only a large UCM is seen
in the chromatogram (Charrié-Duhaut
et al.
2000).
By contrast, the kind of chromatographic features ob-
tained is typically characteristic of a non-weathered
and non-biodegraded oil (Wang
et al.
1998b).
TABLE I.
RECOVERY, RELATIVE STANDARD DEVIA-
TIONS (RSD, %), LIMITS OF DETECTION (LOD)
AND LIMITS OF QUANTIFICATION (LOQ) OB-
TAINED FROM SPIKED SEDIMENT SAMPLES
ANALYSED BY GC-FID
Compounds
% Recovery
±
RSD
LOD
(ng/g)
LOQ
(ng/g)
n-alkanes
66 ng/g
a
116 ng/g
a
C
14
23.3 ± 33.6
31.1 ± 37.4
35.97
65.75
C
15
30.2 ± 22.2
41.3 ± 36.1
25.97
47.65
C
16
49.9 ± 6.7
65.1 ± 13.3
25.76
41.36
C
18
89.1 ± 4.9
97.6 ± 7.9
28.75
37.61
C
19
74.6 ± 4.7
99.4 ± 5.6
27.70
36.63
C
20
88.8 ± 5.0
105.6 ± 7.4
25.89
34.24
C
22
94.0 ± 6.0
97.2 ± 6.0
23.39
31.65
C
23
86.7 ± 7.4
90.4 ±
4.5
22.25
32.04
C
24
85.8 ± 6.6
90.7 ± 6.3
19.26
29.40
C
25
85.5 ± 7.6
93.1 ± 5.2
24.77
35.22
C
26
92.9 ± 8.1
87.6 ± 3.4
19.44
31.76
C
32
79.4 ± 9.7
89.7 ± 8.4
27.75
46.56
PAH
b
NAP
25.6 ± 13.3
33.6 ± 24.3
32.62
82.82
ACE
33.6 ± 13.2
49.1 ± 6.4
17.86
46.64
FLU
57.2 ± 9.3
59.5 ± 8.6
25.70
40.52
DBT
66.9 ± 13.0
74.1 ± 10.4
21.84
38.21
ANT + PHE
56.2 ± 13.5
61.3 ± 18.4
45.87
67.22
FLT
84.2 ± 16.3
88.1 ± 11.9
27.35
36.30
PYR
79.0 ± 15.6
90.2 ± 11.7
16.74
29.98
CRY+B
(a)ANT
76.3 ± 34.4
97.8 ± 11.1
33.60
58.72
B(a)PYR
69.7 ± 32.6
92.1 ± 12.3
20.53
51.31
a
spiked concentrations.
b
Polycyclic Aromatic Compounds: NAP: naphthalene, ACE:
acenaphthene, ±LU: ²uorene, DBT: dibenzothioFene, ANT:
anthracene, PHE: phenanthrene, ±LT: ²uoranthene, PYR:
pyrene, CRY: crysene, B(a)PYR: benzo(a)pyrene.
PETROLEUM HYDROCARBONS ASSESSMENT IN SEDIMENTS OF NORTHEASTERN HAVANA LITTORAL
9
Carbon preference index (CPI) is used in quan-
tifying plant wax contribution versus fossil fuel
contamination (Eglinton and Hamilton 1967, Tulloch
1976). CPI values higher than 4 is commonly associ-
ated to biogenic n-alkanes (Jaffé
et al.
1996, Wang
et al.
2003). In this study, all CPI values in the two
ranges (CPI
C15 – C20
and CPI
C21 – C34
) were around 1,
which is evidence of a major contribution of fossil
fuel hydrocarbons. n-Alkane distributions does not
showed any predominance of nC
27
, nC
29
and nC
31
(
Fig. 4
), usually associated to land-derived organic
inputs transported toward coastal areas (Eglinton and
Hamilton 1967). However, the n-alkane profles oF
samples 12 and 13 accounted for the predominance
of nC
17
in the lower carbon number region (< nC
20
),
which is indicative of the input of marine-derived
hydrocarbons (Blumer
et al.
1971).
The hydrocarbon composition of many aquatic
and photosynthetic bacteria is dominated by the n-
alkane nC
17
(Giger
et al.
1980). This compound has
also been detected in many surface sediments, for
example: in the Rhone and Ebro River, Spain (Dachs
et al.
1999) and in the St. Marys River, Michigan,
USA (Tenzer
et al.
1999). However, the hydrocar-
bon nC
15
, which is usually found in algae (Giger
et
al.
1980), has not been detected in the samples. The
selective degradation or solubilization oF biogenic
markers in the range nC
15
- nC
20
, with respect to the
higher molecular weight homologs has been noticed
(Prahl and Carpenter 1984, Marty
et al.
1994). There-
fore, the low concentration of short-chain n-alkanes
could be attributable to the labile character of these
compounds.
In sample 13 two diFFerent profles are super
-
imposed. One of them characteristic of biogenic
alkanes, with a slight odd carbon number predomi-
nance in the range nC
19
- nC
27
(
Fig. 4
), as well as
the nC
17
prevalence in the lower range indicative of
autochthonous algal input (Gomes
et al.
2003). The
second dominant feature is the pronounced UCM
hump (from ~ nC
17
to nC
34
) representing fossil fuel
contribution (
Fig. 2
). These characteristics suggest
TABLE II.
ALIPHATIC HYDROCARBONS CHARACTERISTIC PARAMETERS DETERMINED IN NORTHEASTERN
HAVANA LITTORAL SAMPLES.
Sampling
sites
1
2
3
4
5
6
7
8
AH (µg/g)
14.0 ± 0.8
a
6.7 ± 0.4
6.3 ± 0.4
4.0 ± 0.3
6.3 ± 0.4
3.1 ± 0.2
2.4 ± 0.2
8.0 ± 0.5
NA (µg/g)
1.96 ± 0.80
0.77 ±
0.10
0.82 ± 0.10
0.54 ± 0.08
1.02 ± 0.11
0.28 ± 0.07
0.10 ± 0.06
0.92 ± 0.11
CPI
nC15-nC20
0.7
0.6
0.6
1.6
0.9
0.5
0.4
1.0
CPI
nC21-nC34
1.1
1.2
1.1
1.3
1.1
1.2
1.5
1.1
UCM (µg/g)
12.0 ± 0.7
5.9 ± 0.4
5.5 ± 0.4
3.4 ± 0.2
5.2 ± 0.3
2.8 ± 0.2
2.3 ± 0.2
7.1 ± 0.4
UCM/NA
6.1
7.6
6.6
6.4
5.1
10.1
22.5
7.7
Pr/Ft
0.6
-
1.1
2.3
0.9
-
-
1.2
nC17/Pr
1.1
-
0.9
1.8
1.8
-
-
1.1
nC18/Ft
1.1
-
1.2
1.1
0.9
-
-
1.2
ArH (µg/g)
10.5 ± 2.1
1.4 ± 0.2
2.3 ± 0.4
n.q
1.1 ± 0.2
n.q
1.3 ± 0.2
3.9 ± 0.7
Sampling
sites
9
10
11
12
13
14
15
AH (µg/g)
17.5 ± 1.0
76.4 ± 4.3
32.7 ± 1.9
23.4 ± 1.4
105.1 ± 5.9
15.0 ± 0.9
11.2 ± 0.7
NA (µg/g)
1.87 ± 0.16
1.22 ± 0.12
1.75 ± 0.15
1.82 ± 0.16
2.37 ± 0.19
0.81 ± 0.10
1.63 ± 0.14
CPI
nC15-nC20
0.7
0.9
1.0
1.5
1.7
0.7
0.5
CPI
nC21-nC34
1.2
1.1
1.2
1.1
1.4
1.1
1.1
UCM (µg/g)
15.6 ± 0.9
75.2 ± 4.2
31.0 ± 1.8
21.6 ± 1.3
102.7 ± 5.8
14.2 ± 0.8
9.6 ± 0.6
UCM/NA
8.4
61.8
17.7
11.9
43.3
17.5
5.9
Pr/Ft
0.6
0.7
1.2
2.2
1.4
0.7
0.5
nC17/Pr
1.1
1.0
1.5
1.4
1.4
1.4
1.1
nC18/Ft
1.4
0.9
1.2
1.2
0.7
1.3
1.1
ArH (µg/g)
6.8 ± 1.3
21.4 ± 4.2
7.1 ± 1.4
20.2 ± 4.0
38.4 ± 7.6
6.3 ± 1.2
4.2 ± 0.8
AH: aliphatic hydrocarbon total concentration; NA: n-alkanes total concentration; CPI
C15 – C20
: carbon preference index (sum
of odd over even n-alkanes in the carbon number range from C
15
to C
20
); CPI
C21 – C34
: carbon preference index (sum of odd over
even n-alkanes in the carbon number range from C
21
to C
34
); Pr: pristane; Ph: phytane; UCM: unresolved complex mixture; ArH:
aromatic hydrocarbon total concentration;
a
: estimated uncertainly; n.q: detected but not quantifed.
E.Y. Companioni Damas
et al.
10
a mixed input of anthropogenic and marine organic
matter, although the high UCM concentration
(
Table II
) justifes that the petrogenic contribution
is the main source.
The isoprenoid hydrocarbons, pristane (2, 6, 10,
14 - tetramethylpentadecane) and phytane (2, 6,
10, 14 - tetramethylhexadecane), are derived from
the diagenetic transformation of phytol and other
isoprenoidyl natural products, and are not primary
constituents of most terrestrial biota (Peter
et al.
2005). However, a higher predominance of pristane
over phytane in sediments can be due to zooplank
-
tonic contribution, particularly of calanoid copepods
which produce it from the phytol in chlorophylla
during their diet (Blumer
et al.
1963, Volkman
et al.
1992). Uncontaminated sediments frequently pres-
ent pristane/phytane (Pr/Ph) ratios higher than 1,
typically between 3 and 5 (Steinhauer and Boehm
C17
C17
C22
C26
C30
C18
C18
C16
C16
Ph
Ph
Pr
Pr
C21
C26
C30
C34
Abundance
1
100
85
75
50
25
0
14.34
27.76
41.19
54.62
68.04
81.47
Time:
Abundance
13
100
85
75
50
25
0
14.34
27.76
41.19
54.62
68.04
81.47
Time:
Fig. 3.
m/85 Mass fragmentograms of samples 1 and 13 showing their composition in n-alkanes and isoprenoid hydrocarbons. Pr: pristane;
Ph: phytane
[mV]
1
100
80
60
40
20
0
0
10
20
30
40
50
[min.]
Time
Voltage
[mV]
3
80
60
40
20
0
0
10
20
30
40
50
[min.]
Time
Time
Voltage
[mV]
Voltage
13
400
300
200
100
0
0
10
20
30
40
50
[min.]
Time
C17
C17
C17
C15
C17
Pr
Pr
Pr
Pr
Ph
Ph
Ph
Ph
C18
C18
C18
C18
C20
C22
C22
C22
C22
C28
C28
C25
C28
C26
C30
C34
[mV]
12
150
100
50
0
0
10
20
30
40
50
[min.]
Voltage
Fig. 2.
Selected gas chromatograms of the aliphatic hydrocarbon fractions of sediment samples collected at Northeastern Havana
Littoral
PETROLEUM HYDROCARBONS ASSESSMENT IN SEDIMENTS OF NORTHEASTERN HAVANA LITTORAL
11
1992). These isoprenoid hydrocarbons were present
in almost all analyzed samples, and the Pr/Ph ratios
were close to 1 (
Table II
). Only the samples 4 and
12 showed Pr/Ph ratios slightly higher (2.3 and 2.2,
respectively), which could be caused by the mixture
of anthropogenic and natural hydrocarbons. This re-
sult corroborates the impact of petroleum residues in
the study area. Finally, the ratios of nC
17
/pristane and
nC
18
/phytane (
Table II
), widely applied as indicators
of oil biodegradation, where in the ranges 0.9 - 1.8
and 0.7 - 1.3, respectively. These values correspond
to non-heavily degraded oil residues (Wang
et al.
1998 a,b), as has been previously stated.
Table III
shows the aliphatic hydrocarbons identi-
fed by GC-MS-TIC in the samples 1 and 13. Besides
n-alkanes and branched alkanes, alkenes were also
identifed. Biogenic alkenes have been widely Found
in sediments and algae (Rowland
et al.
1985, Belt
et al.
2001), and are associated to the production of
marine biogenic material in the aquatic environment.
The hopanes and steranes detected constitute a further
indication of the input of fossil fuel hydrocarbons at
these sites (Faure
et al.
2000), as already suggested
by the existence of UCM and the biomarkers pristane
and phytane. The hopane homologue with the ther-
modynamically more stable 17α(H), 21β(H) confgu
-
ration was also identifed. These hopanes are oF the
most recalcitrant organic compounds from petrogenic
sources Found in the environment (Schwarzbauer
et
al.
2000, Zakaria
et al.
2000).
The total aromatic hydrocarbon concentrations
are shown in
Table II
. These concentrations varied
from 1.1 ± 0.2 to 38.4 ± 7.6 µg/g (dry weight). Higher
levels occurred at sites 10, 12, and 13 located in the
proximity of Jaruco River, where the major oil extrac-
tion operations are carried out.
Lower concentrations
were found for samples 2, 3, 5 and 7. Sites 2 and 3
are situated in the farthest portion of an area used for
oil extraction. Site 5 is near of oil storage facilities.
Site 7 constitutes a strand zone which is more distant
from petrogenic sources.
CONCLUSIONS
The anthropogenic tracers, such as UCM, iso-
prenoid hydrocarbons, steranes and hopanes deter-
mined in this study, revealed that this coastal zone
nC16
Pr
nC24
Ph
nC20
nC22
nC26
nC28
1
nC30
nC32
nC34
0
40
80
120
160
200
Concentration (ng/g)
nC16
Pr
Ph
nC20
3
nC22
nC34
nC24
nC30
nC26
nC32
nC28
0
30
60
90
120
150
Concentration (ng/g)
12
nC16
Pr
Ph
nC20
nC22
nC24
nC26
nC28
nC34
nC30
nC32
0
40
80
120
160
200
Concentration (ng/g)
nC16
Pr
Ph
nC20
nC22
nC24
nC26
13
nC28
nC30
nC32
nC34
0
100
200
300
400
Concentration (ng/g)
Fig. 4.
n-Alkanes and isoprenoid concentration distribution corresponding to the chromatograms displayed in Fig. 4. Bars
represent the estimated uncertainty.
E.Y. Companioni Damas
et al.
12
TABLE III.
COMPOUNDS IDENTIFIED BY GC-MS-TIC IN THE ALIPHATIC FRACTION OF SAMPLES 1 AND 13
No.
Compounds
Typical
RT (min)
Confrmation
ions (m/z)
Samples
1
13
1
n-Pentadecane
19.95
85/212
+
2
1-Tetradecene
23.55
83/196
+
3
n-Hexadecane
23.80
85/226
+
4
2, 6, 10-trimethylpentadecane (norpristane)
25.53
85/238
+
5
1-Pentadecene
25.09
83/210
+
+
6
n-Heptadecane
27.37
85/240
+
+
7
2, 6, 10, 14 – tetrametil-pentadecane (pristane)
27.54
85/268
+
+
8
1-Heptadecene
28.88
83/238
+
+
9
4- Methylheptadecane
29.31
85/254
+
10
3-Methylheptadecane
29.75
85/254
+
11
1-Octadecene
30.53
83/252
+
12
n-Octadecane
30.81
85/252
+
+
13
2, 6, 10, 14-tetramethylpentadecane (phytane)
31.08
85/282
+
+
14
7, 11-Dimethyloctadecane
32.17
85/282
+
15
3-Methyloctadecane
33.08
85/268
+
16
2, 6, 10, 14-tetramethylheptadecane
33.79
85/296
+
+
17
n-Nonadecane
34.11
85/268
+
+
18
4-Cyclohexyltridecane
35.85
85/288
+
+
19
4-Methylnonadecane
36.05
85/282
+
20
3-Methylnonadecane
36.28
85/282
+
21
n-Eicosane
37.27
85/282
+
+
22
7-Propyltridecane
38.40
85/226
+
23
4-Propyltridecane
38.73
85/226
+
24
3-Methyleicosane
39.32
85/226
+
25
n-Heneicosane
40.29
85/296
+
+
26
Allopregnane
41.83
217/218
+
27
n-Docosane
43.17
85/310
+
+
28
5 α-d-Homopregnane
43.85
217/218
+
29
n-Tricosane
45.93
85/324
+
+
30
n-Tetracosane
48.58
85/338
+
+
31
n-Pentacosane
51.12
85/352
+
+
32
Diisooctylftalate
a
52.02
149/390
+
+
33
n-Hexacosane
53.37
85/366
+
+
34
5α, 8α, 14β Cholestane
54.32
217/218
+
35
3-Ethyltetracosane
54.98
85/366
+
36
n-Heptacosane
55.94
85/380
+
+
37
5α, 3 Cholestene
57.95
217/218
+
38
n-Octacosane
58.21
85/394
+
+
39
Scualane
58.46
85
+
40
n-Nonacosane
60.43
85/408
+
41
Stigmastane
61.21
217/218
+
42
5α, 14β, 17β Cholestane
61.44
217/218
+
43
17
α
(H), 21
β
(H) Norhopane
61.80
191
+
+
44
n-Triacontane
62.52
85/464
+
+
45
17
β
(H), 21
α
(H) Norhopane
63.55
191
+
+
46
n-Hentriacontane
64.58
85/436
+
47
n-Dotriacontane
66.56
85/450
+
48
n-Tritriacontane
68.54
85/464
+
49
n-Tetratriacontane
70.41
85/478
+
50
n-Pentatriacontane
72.26
85/492
+
RT: Retention time; AH: Aliphatic Hydrocarbons; +: detected compounds;
a
contamination derived from the laboratory plastic
materials
PETROLEUM HYDROCARBONS ASSESSMENT IN SEDIMENTS OF NORTHEASTERN HAVANA LITTORAL
13
from the Northeastern Havana Littoral received
fossil fuel inputs. The Pr/Ph, CPI and UCM/NA
ratios obtained, lead to the same conclusion. Higher
concentrations were detected in sampling sites sur-
rounded the Jaruco River (Sites 10 - 14) (
Fig. 1
). This
is a direct consequence of the intensive petroleum
exploration occurring at this area.
On the other hand, the aliphatic hydrocarbon
analysis revealed aquatic input in this region. This
biogenic contribution was clearly determined by the
predominant presence of marine - derived hydro-
carbon such as nC
17
and the isoprenoid hydrocarbon
pristane. Anthropogenic and biogenic hydrocarbons
mixture was commonly detected in sediments, with
the prevalence of petroleum-derived compounds. The
infuence oF land material inputs (higher plants) were
not detected in the study area.
REFERENCES
Ahrens M.J. and Depree C.V. (2004). Inhomogeneous
distribution of polycyclic aromatic hydrocarbons in
diFFerent size and density Fractions oF contaminated
sediment from Auckland Harbour, New Zealand:
an opportunity for mitigation. Mar. Pollut. Bull. 48,
341-350.
Barwick V.J. and Ellinson S.L.R. (1999). Measurement un-
certainty: approaches to the evaluation of uncertainties
associated with recovery. Analyst 124, 981-990.
Barwick V.J. and Ellinson S.R.L. (2000). VAM Project
3.2.1. Development and harmonisation of measure-
ment uncertainty principles. Part D: Protocol for un-
certainty evaluation from validation data. Report No:
LGC/VAM/1998/088. LGC (Teddington) Ltd., UK.
Belt S.T., Massé G., Allard W.D., Robert J-M. and Row-
land S.J. (2001). Identi±cation oF a C
25
highly branched
isoprenoid triene in the freshwater diatom
Navicula
sclesvicensis
. Org. Geochem. 32, 1169-1172.
Blumer M., Guillard R.R.L. and Chase T. (1971). Hy-
drocarbons of marine phytoplankton. Mar. Biol. 8,
183-189.
Blumer M., Mullin M.M. and Thomas D.W. (1963). Pris-
tane in zooplankton. Science 140, 974-986.
Burns K.A., Greenwood P.F., Summons R.E. and Brunskill
G.J. (2001). Vertical fuxes oF hydrocarbons on the
Northwest Shelf of Australia as estimated by a sedi-
ment trap study. Org. Geochem. 32, 1241-1255.
Charrié-Duhaut A., Lemoine S., Adam P., Connan J. and
Albrecht P. (2000). Abiotic oxidation of petroleum
bitumens under natural conditions. Org. Geochem.
31, 977-1003.
Dachs J., Bayona J.M., Fillaux J., Saliot A. and Albaigés
J. (1999). Evaluation of anthropogenic and biogenic
inputs into the western Mediterranean using molecular
markers. Mar. Chem. 65, 195-210.
Doriji M., Yamaguchi M., Weisberg S.B., Lee H. J. (2003).
Changing anthropogenic infuence on the Santa Monica
Bay watershed. Mar. Environ. Res. 56, 1-14.
Eglinton G. and Hamilton R.J. (1967). Leaf epicuticular
waxes. Science 156, 1322-335.
Enganhouse R.P. and Pontonillo J. (2000). Depositional
history of organic contaminants on the Palos Verdes
Shelf, California. Mar. Chem. 70, 317-338.
Ezra S., ²einstein S., Pelly I., Bauman D. and Milo
-
slavsky I. (2000). Weathering of fuel oil on the east
Mediterranean coast, Ashdod, Israel. Org. Geochem.
31, 1733-1741.
Faure P. and Landais P. (2000). Natural and anthropic
organic contributions in the sediment of the Kruth-
Wildenstein Lake (Hault-Rhin, France). Géochim./
Geochem. 330, 39-46.
Giger W., Schaffner C. and Wakeham S.G. (1980). Ali-
phatic and ole±nic hydrocarbons in recent sediments
oF GreiFensee, Switzerland. Geochim. Cosmochim.
Acta. 44, 119-129.
Gomes A.O. and Azevedo D.A.(2003). Aliphatic and
aromatic hydrocarbons in tropical recent sediments of
Campos dos Goytacazes, RJ, Brazil. J. Braz. Chem.
Soc. 14, 358-368.
Grossi V., Massias D., Stora G. and Bertrand J.C. (2002).
Burial, exportation and degradation of acyclic petro-
leum hydrocarbons following a simulated oil spill in
bioturbated Mediterranean coastal sediments. Chemo-
sphere 48, 947-954.
Hostettler F. D., Pereira W. E., Kvenvolden K. A., van
Genn A., Luoma S. N., Fuller C. C. and Anima R.
(1999). A record of hydrocarbon input to San Francisco
Bay traced by biomarker pro±les in surFace sediment
and sediment cores. Mar. Chem. 64, 115-127.
Jaffé R., Elismé T., Cabrera A. C. (1996). Organic geo-
chemistry of seasonally flooded rain forest soils:
molecular composition and early diagenesis of lipid
components. Org. Geochem. 25, 9-17.
Jaouen-Madoulet A., Abarnou A., Le Guellec A.-M.,
Loizeau V. and Leboulenger ². (2000). Validation oF
fan analytical procedure for polychlorinated biphenyls,
coplanar polychlorinated biphenyls and polycyclic
aromatic hydrocarbons in environmental samples. J.
Chromatogr. A. 886, 153-173.
Marty J.C., Nicolas E., Miquel J.C. and Fowler S.W.
(1994). Particulate fuxes oF organic compounds and
their relationship to zooplankton Fecal pellets in the
northwestern Mediterranean Sea. Mar. Chem. 46,
387-405.
Medeiros P.M. and Bícego M.C. (2004). Investigation of
E.Y. Companioni Damas
et al.
14
natural and anthropogenic hydrocarbon inputs in sedi-
ments using geochemical markers. I. Santos, SP-Brasil.
Mar. Pollut. Bull. 49, 761-769.
Nuñez A. (2002). Study of Petroleum pollution in cuban
marine ecosystems. MSc Thesis in Environmental
Impact. Instituto de Ciencias y Tecnologías Aplicadas,
Habana, Cuba., Havana, Cuba.
Parrish C.C., Abrajano T.A., Budge S.M., Helleur R.J.,
Hudson E.D. Pulchan K. and Ramos C. (2000). Lipid
and phenolic biomarkers in marine ecosystems: analy-
sis and applications. In:
The Handbook of Environmen-
tal Chemistry: Marine Chemistry
(P. Wangersky ed.),
Springer-Verlag, Berlin, Vol. 5, pp. 194-223.
Peters K.E., Walters C.C. and Moldowan J.M. (2005). The
biomarker guide, Second Edition, Vol. I, Biomarkers
and isotopes in the environment and human history.
Cabridge University Press, New York, 471 p.
Prahl F.G. and Carpenter R. (1984). Hydrocarbons in
Washington coastal sediments. Estuarine Coast. Shelf
Sci. 18, 703-720.
Rowland S.J., Yon D.A., Lewis C.A. and Maxwell
J.R. (1985). Occurrence of 2,6,10-trimethyl-7-(3-
methylbutyl)-dodecane and related hydrocarbons in
the green alga
Enteromorpha prolifera
and sediments.
Org. Geochem. 8, 207-213.
Schwarzbauer J., Littke R. and Weigelt V. (2000). IdentiF
-
cation of speciFc organic contaminants for estimating
the contribution of the Elbe River to the pollution of the
German Bight. Org. Geochem. 31, 1713-1731.
Simoneit B.R.T. and Mazuret M.A. (1982). Organic matter
in the troposphere – II. Natural background of biogenic
lipid matter in aerosols over the rural western United
States. Atmos. Environ. 16, 2139-2159.
Simoneit, B.R.T. (1984). Organic matter of the tropo-
sphere: III. Characterization and sources of petroleum
and pyrogenic residues in aerosols over the western
United States. Atmos. Environ. 18, 51-67.
Steinhauer M.S. and Boehm P.D. (1992). The composition
and distribution of saturated and aromatic hydrocar-
bons in nearshore sediments, river sediments, and
coastal peat of Alaskan Beaufort Sea: implication for
detecting anthropogenic hydrocarbon inputs. Mar.
Environ. Res. 33, 223-253.
Tenzer G.E., Meyers P.A., Robbins J.A., Eadi B.J., More
-
head N-R. and Lansing M.B. (1999). Sedimentary
organic matter record of recent environmental changes
in the St. Marys River ecosystem, Michigan–Ontario
border. Org. Geochem. 30, 133-146.
Tulloch, A.P. (1976): Chemistry of waxes of higher plants.
In:
Chemistry and biochemistry of natural waxes
, (Ko-
lattukudy, P.E. Ed.),Elsevier, Amsterdam, 236 pp.
Volkman J.K., Holdworth D.G., Neill G.P. and Bavor Jr.
H. J. (1992). IdentiFcation of natural, anthropogenic
and petroleum hydrocarbons in aquatic sediments. Sci.
Total Environ. 112, 203-219.
Wang Z. and Fingas M. (1995). Differentiation of the
source of spilled oil and monitoring of the oil weath-
ering process using gas chromatography - mass spec-
trometry. J. Chromatogr. A. 712, 312-343.
Wang Z. and Fingas M.F. (2003). Development of oil hy-
drocarbon Fngerprinting and identiFcation techniques.
Mar. Pollut. Bull. 47, 423-452.
Wang Z., Fingas M., Blenkinsopp S., Sergy G., Landriault
M., Sigouin L., Foght J., Semple K. and Westlake
D.W.S. (1998a). Comparison of oil changes due to
biodegradation and physical weathering in different
oils. J. Chromatogr. A. 809, 89-107.
Wang Z., Fingas M., Blenkinsopp S., Sergy G., Landriault
M., Sigouin L. and Lambert P. (1998b). Study of the
25-year-old nipisi oil spill: persistence of oil residues
and comparisons between surface and subsurface sedi-
ments. Environ. Sci. Technol. 32, 2222-2232.
Wu Y., Zhang J. and Zhu Z. (2003). Polycyclic aromatic
hydrocarbons in the sediments of the Yalujiang Estuary,
North China. Mar. Pollut. Bull. 46, 619-625.
Zakaria M.P., Horinouchi A., Tsutsumi S., Takada H.,
Tanabe S. and Ismail A. (2000). Oil Pollution in the
Straits of Malacca, Malaysia: Application of molecular
markers for source identiFcation. Environ. Sci. Tech
-
nol. 34, 1189-1196.
Zegouagh Y., Derenne S., Largeau C., Bardoux G. and
Mariotti A. (1998). Organic matter sources and early
diagenetic in Arctic surface sediments (Lena River
delta and Laptev Sea, Eastern Siberia) II. Molecular
and isotopic studies of hydrocarbons. Org. Geochem.
28, 571-583.
logo_pie_uaemex.mx