Marine Pollution Bulletin xxx (xxxx) xxxxxx

Contents lists available at ScienceDirect

Marine Pollution Bulletin

journal homepage: www.elsevier.com/locate/marpolbul

Baseline

Levels and sources of heavy metals and PAHs in sediment of Djibouti-city

(Republic of Djibouti)
Moussa Mahdi Ahmeda,, Pierre Doumenqc, Mohamed Osman Awaleha, Agung Dhamar Syaktib,e,
Laurence Asiac, Serge Chirond
a
Institut des Sciences de la Terre, Centre d'Etude et de Recherche de Djibouti, Route de l'aroport BP 486, Djibouti, Republic of Djibouti
b
Center for Maritime Bioscience Studies-Institute for Research and Community Service, Jenderal Soedirman University, Jl, Dr, Suparno, Purwokerto 53123, Indonesia
c
Laboratoire de Chimie de l'environnement, Equipe Micropolluants Organique, FRE-CNRS 3416, Europle de l'Arbois-Btiment Villemin BP 80, Aix en Provence Cedex 4,
France
d
UMR HydroSciences 5569, Montpellier Universit, 15 Avenue Ch, Flahault, 34093 Montpellier Cedex 5, France
e
Marine Science and Fisheries Faculty, Raja Ali Haji Maritime University, Jl. Politeknik Senggarang-Tanjungpinang, Riau Islands Province, 29100, Indonesia

A R T I C L E I N F O A B S T R A C T

Keywords: Selected heavy metals and polycyclic aromatic hydrocarbons (PAHs) were determined in marine sediment from
Red sea 28 sites Djibouti city. The concentrations of trace elements varied from 0 to 288.1 mg/kg with relative
Marine sediments abundance of trace metals in sediments was in the order of Zn > Cu > Ni > Cr > Co > Pb > Cd. Zn, Cu
PAH's and Ni exceeded consensus based sediment quality guideline values 7, 14, 15 sites respectively. Enrichment
Heavy metals
factor and pollution load index showed relatively low to moderate contamination. The concentrations of total 16
Enrichment factor
PAHs varied widely depending on the sample location and ranged from 2.65 to 3760.11 ngg 1, with the mean
Diagnostic ratio
concentration value of 387.87 ngg 1. Compositions and relative abundance of individual PAH using molecular
diagnostic ratio using congener's m/z 178 and 202 indicated pyrolytic origin and reecting a petroleum
combustion, grass/wood and coal combustion and a petrogenic source. This study represents the rst pollution
baseline and a reference for future studies in Djibouti.

The contamination of the marine environment with organic and
inorganic contaminants is a major concern (Islam and Tanaka, 2004).
Red sea appears to suer from high anthropogenic pressure due to
inputs from industrial, sewage euents, shipping activities, spillage
coastal activities and natural seeps (Dou Abul et al., 1998; Khalaf and
Kochzius, 2002; Kress et al., 1999; Nemr et al., 2005; Walker and
Ormond, 1982). It leads to contamination of the surrounding area not
only by organic compounds (e.g. polycyclic aromatic hydrocarbons,
PAHs) but also to heavy metals such as Cr, Ni, Cu, Zn, As and Pb
(Fiedler et al., 2009; Ugochukwu and Leton, 2004). Furthermore coastal
sediments act as temporary or long-term sink and is one of the most
important reservoirs of environmental pollutants.
Heavy metals occur naturally in the ecosystem at various levels of
concentrations. Some heavy metals are essential for biological function
in trace concentrations such as Cu, Cr, Mn, Zn and Co while high
concentrations of essential element have adverse eects on living
organism (Hogan, 2010). Metals bioaccumulating in the food chain
pose a risk to human exposure and damage to predators (Amundsen
et al., 1997; El-Moselhy et al., 2014; Muchuweti et al., 2006).
On the other hand polycyclic aromatic hydrocarbons (PAHs) are an
important class of persistent organic pollutants in the marine environ-
ments, particularly in estuaries, harbors and shallow coastal areas
exposed to anthropogenic inputs e.g. a renery site (Barakat et al.,
2011; Baumard et al., 1998; Ne, 1985; Nemr et al., 2005; Syakti et al.,
2013). Anthropogenic sources of PAHs in the marine environment are
generated through incomplete combustion (e.g. coal, petroleum and
wood) or derived from crude and rened petroleum products (oil spills,
routine tankers operations, oil exploitation, etc.). PAHs hazardous
property, lipophilicity, low water solubility and adsorption to marine
particles and sediments make them a group of chemicals that may aect
wildlife and humans via the food chain which prompted US EPA to
include 16 PAHs within the priority pollutants list (Manoli et al., 2000).
PAHs are known to have adverse eects on humans and the environ-
ment through mechanism of carcinogenesis (IARC, 2010) as well as
acute and developmental toxicity has been observed in the aquatic
environment (Ne, 1985).
Several data is available from Yemen, Egypt, Sudan and Saudi
Arabia (Al-Shwa, 2003; Aly Salem et al., 2014; Ashraf and Salam,
2012; Barakat et al., 2011; Bejarano and Michel, 2010; Dou Abul et al.,
1998; El Nemr et al., 2007; Jahin et al., 2009; Jiries et al., 2003; Khairy

Corresponding author.
E-mail address: moussa.mahdi@chemist.com (M. Mahdi Ahmed).

http://dx.doi.org/10.1016/j.marpolbul.2017.05.055
Received 11 April 2017; Received in revised form 19 May 2017; Accepted 22 May 2017
0025-326X/ 2017 Elsevier Ltd. All rights reserved.

Please cite this article as: Ahmed, M.M., Marine Pollution Bulletin (2017), http://dx.doi.org/10.1016/j.marpolbul.2017.05.055
M. Mahdi Ahmed et al. Marine Pollution Bulletin xxx (xxxx) xxxxxx

!
M11 .
M2
!
DJN-01
M7 !
!
M2B
! DJN-06
!

Djibouti
M4 M8 PDj-01
! ! ! city
PDJ-09
! M13
!
PDJ-05
! M12B
PDJ-07 !
!
M3
! MV-10 MV-06
! ! ! MV-02
OBOCK
MV-21' ! ! MV-01
MV-15
! MV-03'
!
TADJOURAH M1
MV-19 !
! DJE-02
MV-18 !
!

Am
MV-23

b
DJIBOUTI

ou
li d
ARTA

ry
DIKHIL

r ive
ALI SABIEH
MV-24

r
!

0 0,75 1,5 3 Km Source: CERD

Fig. 1. Map of sampling stations (n = 28) in the East and West coast of Djibouti-city.

et al., 2009). Despite the signicance of this coast, to the best of our
knowledge this area has never been investigated in detail for organic
contaminants and heavy metals both occurring naturally and anthro-
pogenically, which may enter into the marine ecosystem from various
point sources.
The present study is the rst investigation of the current status of
PAHs and heavy metal concentration in surface sediments of Djibouti-
city coastal area. The results provide a valuable reference data set for
environmental managers.
Djibouti city is located at 1130N, 4300E in the Horn of Africa,
Fig. 1. shows the general outline of the Republic of Djibouti. It has a
very hot and humid yet rainless summers (42 C and less 215 mm
annual precipitation) and warm winter season (21 C). The semi-
enclosed nature of the Red Sea limits the opportunity for renewal of
the water mass. The coastline is composed of a mixture of eluvial and
colluvial deposits, taluses, sheet oods, dunes and beach deposits with
tidal range is 03 m relative to Chart Datum (Schlter, 2008). The
monsoon wind vary from North-East during winter and South-West
during summer season. Increasing activity in the capital has caused oil
spills due to accident, chronic release of industrial contaminants mostly
untreated. Furthermore untreated or insuciently treated wastewater
is discharged into the sea.
Surcial sediment samples (010 cm, n = 28) based on their
dierent potential levels and sources of contamination used in this
study were collected in Djibouti-city from January to April 2016. The
sampling time coincides with an intense activity of Ambouli Wadi (dry
river) which renewed surface sediment in Djibouti bay. The landmarks
in the adjacent land areas to the sampling sites were recorded and all
sampling sites were dened using global positioning system (Table S1).
Twelve samples were collected in Djibouti-city bay, eleven stations
were collected in Djibouti-city mangrove and ve samples in the
recreational and tourism area. Sediments along the shore were collected
by foot while sediments from the bottom sea (250 m) were collected
using a diver with an adequate container and stored at 4 C during
transportation to the laboratory. Sediment samples were dried at 30 C
in a ventilated air drying oven and subsequently sieved to < 2 mm
and < 0.15 mm for polycyclic aromatic hydrocarbons (ISO
15527:2008) and heavy metal (ISO 11466:1995) determination respec-
tively.
High purity ICP selected heavy metals standard solution (1000 ppm)
was obtained from Horiba (Jobin Yvon, France). Hydrochloric and
nitric acid (70%) were of analytical grade (Sigma-Aldrich). All the
organic solvents used for the analysis n-hexane, dichloromethane and
acetone were of HPLC grade (Sigma Aldrich). Mixture standards (PAH
Mix, EPA), individual surrogate and internal standards (phenanthrene-
d10, pyrene-d10, chrysene-d12) were obtained from Sigma Aldrich for
identication and quantication of PAHs. Dichloromethane, n-pentane,
n-hexane, (VWR, France) for PAH extraction and clean-up were of HPLC
grade. Silica gel-60 (200300 mesh), alumina (200300 mesh) and
copper powder (> 230 mesh) were purchased from VWR
International (France). Certied Reference Material NIST 1941b
PAHs, PCBs and pesticides on Fresh Water Sediment and IAEA-158
were purchased from Sigma-Aldrich and International Atomic Energy
Agency respectively. All glassware for metal analysis was acid washed
while for PAH analysis was rinsed in dichloromethane followed by
acetone to remove organic residues (Fig. 2).
Metals extraction from sediment was performed according to
procedure described by ISO 11466. Briey, 3 g the dried sediment at
105 C was transferred to Kjeldahl tubes and was left overnight after the
addition of 21 mL of hydrochloric acid and drop by drop addition of
7 mL nitric acid solution followed by 15 mL of nitric acid. In a Kjeldahl
block, the suspension was reuxed for 2 h. After reux, the tube were
let to reaching room temperature, the suspension was ltered using
0.45 m membrane while thoroughly rinsing the digestion tubes with
30 mL milliQ water (< 18 m/cm). The ltrate was quantitatively
transferred to a 50 mL volumetric ask and analyzed.
PAH's extraction was performed accelerated solvent extraction with
a Dionex ASE 200. A 33 mL extraction cell was packed with two
cellulose lter, glass bers (pre-cleaned by heating at 450 C over night)
and the spiked sediment Briey 5 g of nely sediment previously sieved
at 2 mm were spiked with deuterated surrogate standards, Ph-d10 and
Chr-d12. The extraction cell was left for 20 min to make sure of full
percolation through the sample. Extraction conditions were as follow:
100% DCM was used as solvent and a temperature of 100 C. The heat
up time was 5 min and the program had ve static cycles with 2 min
extraction time at a pressure of 1500 psi and a ush volume of 35%
(Tronczyski, 2005). The sediments samples were extracted in two vials
which were combined and pre-concentrated to < 5 mL under a gentle
stream of nitrogen. Sulfur interference was removed by shaking the
extract with copper powder previously activated with 10% HCl and
washed ve times with dichloromethane and n-hexane. The extracts
were evaporated to dryness and solvent exchanged to n-heptane in
order to purify and fractionated on alumina:silica (1:1, w:w) column to
eliminate organic interferences. The extracts were then concentrated to

2
M. Mahdi Ahmed et al. Marine Pollution Bulletin xxx (xxxx) xxxxxx

450,0

400,0

350,0
Metal Concentrations (mg/kg dw)

300,0
Zn
250,0 Pb
Ni
200,0 Cu
Cr
150,0
Co
100,0 Cd

50,0

0,0

Fig. 2. Metal concentrations in Djibouti-city sediment expressed in mg/kg dw.

1 mL with a rotary evaporator prior to the addition of Pyr-d10 as an
internal standards.
pH was measured after 1 h stirring of a soil:ultrapure water with a
1:5 ratio (NF ISO 10390, pH meter PC650, Eutech Instruments).
Sediment organic carbon is based on Walkley-Black chromic acid wet
oxidation method (Walkley and Black, 1934) and pipette method was
used for particle size distribution (Day, 1965).
Trace metals levels were measured by an inductively coupled
plasma atomic emission spectrometer (ICP-AES, Ultima 2 Horiba
Jobin Yvon) after acid digestion. Blank samples were prepared and
treated exactly in the same way as the samples. Instrument calibration
standards were prepared using mono-element certied reference solu-
tion (Merck). The DLs were in the range of 0.010.08 mg/kg for
selected metals. Certied reference material IAEA-158 was used to
validate analysis and measured values average ranged between 80%
and 101% (Table S3). Analytical residual standard deviations on
triplicate samples were between 2 and 6%.
PAHs analysis were conducted on a capillary gas chromatography
coupled with mass spectrometry (GCMS; Autosystem XL GC and
TurboMass from Perkin Elmer, USA) equipped with an Elite 5MS
capillary column (Perkin Elmer, 30 m 0.25 mm 0.25 m lm
thickness). Chromatographic conditions were as follows (Kanzari
et al., 2014): splitless injection (30 s) and PSS injector programmed
from 50 C to 250 C for 1 min to reduce solvent peak with a constant
ow of Helium at 1 mLmin 1. For PAH, the oven temperature was as
follows: from 40 C (held for 2 min) to 120 C (45 Cmin 1) to 310 C
(5 Cmin 1) and followed by an isothermal for 20 min at 310 C.
16 US EPA priority PAHs were quantied using surrogates (phenan-
threne-d10, m/z 188 and chrysene-d12, m/z 240) and internal standard
(pyrene-d10). All data were subject to procedural and matrix blanks.
Procedural blanks were carried out between each batch of ve samples
and no contamination was observed. Matrix blanks were performed
following the same procedures used for samples. Individual mass of
each PAH in the blanks was insignicant relative to sediment samples.
The mean recoveries (%) for surrogates in the sediment samples were
84% to 102% for PAH. The relative standard deviation (RSD) for PAH
ranged between 0.9%4.6% and the detection limits of PAH with a
signal to noise ratio of 3 were 0.010.18 ngg 1 dw (Table S8)
An overall assessment of sediment was used to evaluate the level of
metal contamination from natural and anthropogenic sources in
Djibouti. Three approaches, (i) enrichment factor, (ii) contamination
factor and pollution load index were determined.
Enrichment factor (EF) was applied to investigate the degree of
sediment metal contamination compared to background as well as to
dierentiate metal source originating from anthropogenic and natural
means (Ergin et al., 1991). It involves normalization of selected metals
with respect to a reference element such as Al, Fe and Mn (Karbassi
et al., 2008). Fe was used as a normalizer because it is rich in earth crust
and assuming that it is free of anthropogenic impact. The EF was
calculated using the following equation:
Me
( Fe ) sample
EF (Me) = Me
( Fe ) Background (1)
Me
where ( Fe ) sample represents the ratio of concentration of selected
Me
metals to that of Fe in stations of study and ( Fe ) Background is the same
ratio of the background concentrations.
Contamination factor (CF) determines the level of sediment anthro-
pogenic metals contamination and calculated according to (Hakanson,
1980):
(Me) sample
CF (Me) =
(Me) Background (2)
where (Me)sample represents the concentration of selected metals in
samples and (Me)Background is the background value of that element.
The background levels used to calculate EF and CF were Fe
(47,200 mg/kg), Cr (90 mg/kg), Cu (45 mg/kg), Zn (95 mg/kg), Pb
(20 mg/kg), Co (90 mg/kg), Cd (0.3 mg/kg), Ni (68 mg/kg) reported
for sedimentary rocks were considered as background values (Turekian
and Wedepohl, 1961).
The pollution load index (PLI) is a tool that investigates the pollution
status of dierent samples in the study area using the following
equation (Tomlinson et al., 1980):
PLI = (CF1 CF2 CF3 CFn )1 n (3)
where n is the number of studied metals and CF is the calculated
contamination factor.
Classication of EF, CF and PLI limits indicating low, moderate and
severe contamination were summarized in Table 1.
Diagnostic criteria used in the identication of PAH sources and
origin were Ant/(Ant + Phe), Fl/(Fl + Pyr), BaA/(BaA + Chry), IP/
(IP + BghiP), BaA/Chry and IPyr/BghiP and summarized in Table 1.

3
M. Mahdi Ahmed et al. Marine Pollution Bulletin xxx (xxxx) xxxxxx

Table 1
Characteristics heavy metal pollution assessment and PAH molecular diagnostic ratios.

Heavy metals

Natural sources Anthropogenic sources Low Minor Moderate Moderate severe Severe Extreme severe

EF < 1.5 > 1.5 <1 <3 35 510 1025 2550

CF <1 13 36 >6
PLI <1 >1

PAHs

Petrogenic Pyrogenic Fuel combustion Grass/coal/wood combustion

Ant/(Ant + Phe) < 0.1 > 0.1

Fl/(Fl + Py) < 0.4 > 0.5 0.40.5 > 0.5
BaA/(BaA + Chry) < 0.2 > 0.35
IP/(IP + BghiP) < 0.2 > 0.5 0.20.5 > 0.5

Sediment characterization provides important data on its prove-
nance, depositional condition and transport history. Table S2 shows the
physico-chemical characteristics (grain size, organic carbon, etc.) of
sediment collected in Djibouti-city. Sediment are classied in the
dierent classes from sandy to loamy with low organic matter content
(616.2%). Table S4 represents the range and average values of the
major elements (Al, Fe, K, etc.) in the sediments of Djibouti-city.
All measured concentrations for selected metals can be found in
Table S5. The minimum and maximum concentrations of trace elements
were 0.3288.1 mg/kg (Zn), 172.2 mg/kg (Cu), 0.839.7 mg/kg (Ni),
1.963 mg/kg (Cr), 0.444.7 mg/kg (Co), 0.744.8 mg/kg (Pb) and
00.4 mg/kg (Cd). The relative abundance of sediments was in the
order of Zn > Cu > Ni > Cr > Co > Pb > Cd. Consensus based
sediment quality guideline (CSBQG) values for selected metals are also
shown in Table S5. CSBQG values are given as threshold eect levels
(TELs) for which it is not expected that harmful eects will occur
(MacDonald et al., 2000). The pollution level of Djibouti-city is
compared to CSBQG values in order to evaluate the environmental
concern. Cd, Co, Cr and Pb measured values did not exceed the CSBQG,
whereas the concentration of Zn, Cu and Ni exceeded CSBQG values.
For Zn, 7 sites (M3, M8, DJN-01, MV01, MV-06, MV-10, and MV-15), Ni
concentration exceeded in 15 stations and Cu concentrations exceeded
in 14 stations. M3, M4, M8, MV01, MV03, MV03, MV06, MV10, MV18,
MV21, MV23 and MV24 stations exceeded the concentration of Cu and
Ni respectively.
Metals naturally occur in earth crust (Turekian and Wedepohl,
1961), due to dierences in mineralogy of geological formations,
sediment genesis aects background concentration of heavy metals in
sediments. Table 2 presents levels of the investigated metals in others
coastal sediment in the Red Sea, Mediterranean Sea and Pacic Ocean.
It is observed that Djibouti-city has low to intermediate levels of
selected metals similar to sediment of the Red Sea. Izmir Bay, Toulon
bay and Naples Port have the highest concentration of selected heavy
metals which corresponds to the knowledge that the Mediterranean Sea
is highly aected by anthropogenic pollution. The CSBQG TEL values
are exceeded for Cu (n = 15), Ni (n = 15) and Zn (n = 6) but Cd
values were below CSBQG TEL for all sediment samples.
Heavy metals released into the marine environment binds to
particulate matter and marine sediments act as an ultimate sink for
heavy metals. Hence heavy metals tend to accumulate into sediments
and are represented by the contamination Factor (CF), Pollution Load
Index and Enrichment Factor (EF) reported in Table 3. CF estimates the
level of sediment contamination and is the initial step in the calculation
of PLI (Eq. (3)) which determines the overall metal accumulation in a
specic site. According to the calculated CF values, almost all the sites
(n = 26) showed low contamination for Cr, Ni, Cd and Pb with limits
reported in Table 1. The only station that presented moderate pollution
for Pb and Cd was MV-01 which corresponds industrial wastewater
discharge site. In addition six stations (i.e. MV-01, MV-10, etc.) showed
signs of moderate contamination for Cu (Table S6). Zn contamination
factor showed moderate pollution for M3, M8, DJE02, etc. It was clear
from calculated PLI that MV-01 sediment was in progressive pollution
situation (PLI > 1), all other sediments (n = 26) low heavy metal
loading. The accumulation of Zn at sites M8 and DJE-02 with CF > 2
could be attributed to the combined eects of sewage discharges and
the electrical power station.
Enrichment of metals normalized with their background values
indicated either a natural (EF < 1.5) or an anthropogenic (EF > 1.5)
sources as stated in Table 1. Generally, the EF showed a low to minor
heavy metals concentrations except in certain hot spot. Great EF at M3,

Table 2
Concentration range of selected metals in Djibouti-city sediment. For comparisons, levels from other marine sediment in dierent region. Macdonald's consensus based sediment quality
guideline values for threshold eect levels (CSBQG TELs) are shown in mg/kg dw.

Site PAH concentration (ng/g dw) References

Cd Cr Cu Pb Ni Zn Co

Saudi Arabia, Jazan 0.5 9.6 16.4 3.9 44.3 24.7 Mortuza and Al-Misned (2017)
Yemen, Jeddah 3.083.51 12.922.8 17.523.8 80.398.7 67.885.5 52.7 Badr et al. (2009)
Egypt 21.4 51.4 Okbah et al. (2005)
Sudan, Port Sudan 10.3122.8 3.926.7 80.8130.3 19146.5 Idris et al. (2007)
Italy, Naples 0.22.5 10.3161.8 40415 37314 411196 1.97.2 Adamo et al. (2005)
France, Toulon bay 0.052.9 8.512.1 5.8846 14.9469 8.837.6 24.31340 Tessier et al. (2011)
Turkey, Izmir Bay 13.528 38.9112.4 55.2172 4401900 Caccia et al. (2003)
USA, Florida Bay 57347 4.95.4 Pekey (2006)
Australia, Port Jackson 0.0224.3 9.51053 37.93604 5.0245 1087622 2.254 Birch and Taylor (1999)
Djibouti-city 00.4 1.963 172.2 0.744.8 0.839.7 0.3288.1 0.444.7 This study
CSBQG, TEL 0.99 43.4 31.6 35.8 22.7 121 MacDonald et al. (2000)

4
M. Mahdi Ahmed et al. Marine Pollution Bulletin xxx (xxxx) xxxxxx

Table 3
Minimum, maximum and mean value of Enrichment factor normalized by Fe,
Contamination factor (CF) and Pollution Load Index (PLI) in sediment from Djibouti-city.

Min Max Mean Number of samples exceeding limit

EF (Cu) 0,01 1,8 0,7 1

EF (Zn) 0,00 3,2 0,9 7
EF (Pb) 0,02 1,8 0,3 1
EF (Cr) 0,01 0,7 0,3 0
EF (Co) 0,07 7,6 0,9 3
EF (Ni) 0,02 1,1 0,3 0
EF (Cd) 0,00 6,0 0,7 1
CF (Fe) 0,09 7,9 1,4 18
CF (Cu) 0,02 1,6 0,7 7
CF (Zn) 0,00 3,0 1,0 14
CF (Pb) 0,03 2,2 0,3 1
CF (Cr) 0,02 0,7 0,3 0
CF (Co) 0,02 2,4 0,8 9
CF (Ni) 0,01 0,6 0,3 0
CF (Cd) 0,01 1,3 0,4 1
PLI 0,04 1,2 0,6 1
Fig. 3. Distribution of polycyclic aromatic hydrocarbons of 23, 4- and 56-rings in
marine sediment.

M8, MV-01 and DJE-02 for Zn (Table S6) which is a typical anthro-
pogenic metal aected by humans activity can be attributed to surface
run-o and input organic wastes from municipal sewage and solid
wastes. In addition, the low enrichment of Pb revealed no anthropo-
genic sources of these metals related to automobile activities or leakage
of leaded gasoline into coastal waters. The Pearson correlation matrix
represented in Table S7 revealed a high coecient amongst some trace
metals such as Zn, Ni, Cu, Cr, Co and Cd. These results indicate that
such elements have a similar occurrence and a similar pattern of
distribution. However trace metals in general are negatively correlated
with organic carbon except for Cd and Pb. On the other hand Cr and Ni
are inuenced and accumulated by sediment clay. Analysis of heavy
metals in sediments oers more convenient and more accurate means of
detecting and assessing the degree of water pollution (Tam and Wong,
2000). The accumulation of pollutants is likely to increase and aecting
aquatic life taking into account the Red Sea is an enclosed water body
with a slow turnover of 200 years (Morcos, 1970).
The concentrations of total 16 PAHs varied widely depending on the
sample location and ranged from 2.65 to 3760.11 ngg 1, with the
mean concentration value of 387.87 ngg 1 (Table S9.). The highest
values were found in sample MV-01 in the mangrove area near the
output of an industrial complex and in sample M8 at proximity of the
previous oil terminal. The minimum content of total 16 PAHs was found
in station DJN-06 located near a hotel. > 32% of the sites had a total
content of PAHs > 200 ngg 1. On the basis of classication adapted
by (Baumard et al., 1998), the sediment samples from coastal areas of
Djibouti-city can be considered low to moderate polluted regarding
PAHs. Thirteen samples had values of 16 PAHs lower than 100 ng/g 1
indicative of low pollution whereas value higher than 1000 ngg 1
were reported for two stations corresponding to chronically polluted
industrialized area and harbors. Station MV-10 and MV-6 are located
near the mouth of the Ambouli Wadi (dry river) intermittent stream. The
pollution in this area is aected agriculture runo and input of
automotive waste euent. Stations M2, M2B, M8 and M7 are located
in Djibouti-bay where heavy trac of tankers and commercial cargo
boats are frequent. It is estimated that > 3, 978,992 m3 of oil leaked
under Djibouti port from 1997 to 2014 (Caminiti, 2010). Samples DJN-
01 and DJN-06 from pristine region with no wastewater discharge or
industrial activities contained less PAH content. The distribution of
PAHs concentration created a spatial pattern which indicated that the
lake is aected by dierent sources of PAHs.
PAHs main sources in environmental system originate mainly from
pyrolytic or petrogenic sources. Pyrolytic PAH contains four or more
aromatic rings while unburned petroleum contains less than four
aromatic rings (Baumard et al., 1998). Compositions and relative
abundance of individual PAH in the investigated sediments were more
or less quite similar, spatial patterns which indicated that the study site
is aected by dierent sources of PAH. The PAH composition prole is
shown in Fig. 3. PAHs with 23 rings (Low Molecular Weight, LMW) are
most abundant in stations M1, M12B, M2B, M7, M8, PDJ-9, MV-23,
PDJ-1 and DJN-06. At PDJ-09 was found the highest ratio of 23 rings
which corresponds with knowledge that a petroleum leak in the oil
terminal. Furthermore, 46 ring PAHs (High Molecular Weight, HMW)
were abundant at other stations in particular M3, MV-06 and MV-15. At
M3, the highest ratio of 46 rings was observed which indicated that
this site is aected by pollution from incomplete biomass and fossil fuel
combustion.
On average HMW dominated the sediment composition. Feng et al.
(2016) observed that due to high log Kow of HMW compounds, they
could easily accumulate and remain for long period in sediment. The
abundance of HMW could reect the presence of high temperature
combustion from pyrogenic sources (i.e. coal, vehicles, etc.) (Yunker
et al., 2002). Other factors including physicochemical properties of
sediment aect the level of PAH (Feng et al., 2016; Scheibye et al.,
2014). Sediment organic carbon has particularly been considered as an
important factor controlling PAH distribution in sediment. Organic
carbon (%) was determined and ranged from 6.6 to 14.9%. However
there was no observed correlation (R2 = 10.6%) between PAHs con-
centration and organic carbon (data not shown). In Djibouti-bay (West
of Djibouti-city), high current from the Ambouli Wadi can erode the ne
sediments and suspend them into the water column.
Sources of PAHs in the environment in marine sediments belong to
three categories: petrogenic, pyrogenic and biogenic based upon the
predominance of dierent PAHs congeners. Although preliminary
conclusions point to the pyrogenic origin of PAHs. Oyster conducted
an oil seeps survey in 2012 using gravity and magnetics data for a
qualitative structural interpretation of Djibouti area during which they
identied pollution slicks on the sea surface of Djibouti-bay and
mangrove (Oyster, 2012).
PAH congeners of m/z 178 (Ant and Ph) and 202 (Fl and Py) are
widely used to dierentiate between pyrolytic and petrogenic sources
(Fig. 4). Yunker et al. (2002) determined that more denitive inter-
pretations is led by the ratio Fl/(Fl + Pyr) due to the greater thermal
stability of the isomers. Petroleum combustion sources are character-
ized by Ant/(Ant + Ph) > 0.1 and 0.4 < Fl/(Fl + Pyr) < 0.5
(Kanzari et al., 2014). Considering Ant/(Ant + Ph) ratio, all site values
ranged between 0.12 and 0.28 which conrmed a pyrolytic origin
(Fig. 4). Fl/(Fl + Pyr) diagnostic ratio twelve sample including stations
M12B, M11 DJE-02 and MV-02 indicated pyrolytic origin and reecting
a petroleum combustion source. The area has predominantly combus-
tion origin from liquid fossil fuel most likely from marine activities.

5
M. Mahdi Ahmed et al. Marine Pollution Bulletin xxx (xxxx) xxxxxx

cene at the same site, MV-01. The concentrations of PAHs in sediments

Fig. 4. Diagnostic ratio plots of Fl/(Fl + Pyr) vs Ant/(Ant + Phen).
Seven stations ranged from 0.55 to 0.8 suggesting that PAHs originated
from grass/wood and coal combustion. Most of those sites corresponds
to mangrove area which was burnt in the 8090s. Eight stations mostly
located in Djibouti-bay with a Fl/(Fl + Py) ratio < 0.4 indicating a
petrogenic source of PAH. This area has been subjected to a petroleum
input since 1997 and is a major shipping thoroughfare. There is a huge
number goods transporting and tourist boats which could explain the
petrogenic source.
The sediment quality guidelines are being used by various federal
and provincial agencies in North America in order to protect freshwater
and marine ecosystems (Long and MacDonald, 1998; MacDonald et al.,
2000). Variables of quality for Sediment containing organisms were
classied into dierent categories: Threshold eects levels (TELs),
eect range low values (ERLs) probable eect levels (PELs) and eect
range median values (ERMs). Table 4 also lists the consensus based
sediment quality guidelines (CBSQG) values for selected polycyclic
aromatic hydrocarbons as threshold eect concentration (TEL)
(MacDonald et al., 2000) and presents studies on PAHs in the Red sea
and Gulf of Aden. CBSQG values were exceeded by Naphthalene,
Fluorene, Phenanthrene, Anthracene, Chrysene and Benzo[a]anthra-
of Djibouti were relatively higher than those in some areas of the Red
Sea and the Gulf of Aden. Egypt has the highest levels of F, P, Fl, Py,
BaA, Ch and BaPy which corresponds well with anthropogenic hydro-
carbon inputs associated with industrial discharges (petroleum distri-
butor and renery), shipping activities (dry docking), and sewage
outfalls (sewage).
The present study evaluated the degree of heavy metal and
polycyclic aromatic hydrocarbon pollution in the coast of Djibouti city.
Heavy metals pollution of sediments was assessed for 28 sites and the
results indicated that Cu (n = 15), Ni (n = 15) and Zn (n = 6)
exceeded consensus-based sediment quality guidelines in several sta-
tions. Results indicated that Zn was the most enriched metal in six
stations as consequence of human activities from surface run-o and
input organic wastes from municipal sewage and solid wastes.
Contamination factor and pollution load index values indicated that
Djibouti city sediment showed load metal loads in comparison to other
sites in the Red or Mediterranean Sea. It was observed that Djibouti-city
has low to intermediate levels of selected metals similar to sediment of
the Red Sea. The concentrations of total 16 PAHs varied widely
depending on the sample location and ranged from 2.65 to
3760.11 ngg 1. More than 32% of the sites had a total content of
PAHs > 200 ng/g which can be considered low to moderate pollution
PAHs. Sources of PAHs were determined by the molecular diagnostic
ratio of Ant/(Ant + Ph) vs. Fl/(Fl + Pyr). Eight stations mostly located
in Djibouti-bay with a Fl/(Fl + Py) ratio < 0.4 indicating a petrogenic
source of PAH. There is a huge number goods transporting and tourist
boats which could explain the petrogenic source.
During our sampling period, Ambouli Wadi was running and hence
the low level of contaminant could come from the Wadi's water renewing
the upper layer sediment. However the present results provide baseline
information on the metal and PAH pollution in Djibouti city against
which future anthropogenic eects could be assessed. A few hotspots
were identied, hence these sources are under investigation and the
quality of sediment monitored. Furthermore, we recommend including
nutrients that may cause eutrophication, n-alkanes, PCBs and pesticides
in future monitoring programs. To the best of our knowledge, it is the
rst study on Djibouti city, it could be used as a contribution to the
knowledge and rational management of this region.

Table 4
Concentration ranges of selected polycyclic aromatic hydrocarbons (ng/g dw) in Djibouti-city marine sediment (n = 28) in comparison with Mediterranean or Red sea region and
consensus based sediment quality guidelines values for threshold eect concentrations (CSBQG TELs).

Site PAH concentration (ng/g dw) References

N Acy Ace F P A DBahAnt Fl Py

Hadhramout, Yemen 07.66 00.87 00.44 01.30 0.2415.47 010.06 02.02 043.33 039.71 Mostafa et al. (2009)
Suez Gulf-Egypt 0.049.15 0.272.68 0.024.64 0.060.99 1.689.98 0.3316.16 1.654.03 1.411.04 Aly Salem et al. (2014)
Red Sea-Egypt 025.4 0710.1 0232.2 0173.7 0303.4 048.1 03158 01518.8 Nemr et al. (2005)
Abu Qir Bay, Egypt 037.4 025.8 035.6 0496 0470 0211 0357 0490 Khairy et al. (2009)
Sardinia, Italy 0320 0215.3 0421.2 0410 0967 0102 0325 0625 0944 Schintu et al. (2015)
Levantine Basin, Israel 1.44 0.71.2 1.87.1 0.61.7 0.81 0.71.2 1.66.2 Astrahan et al. (2017)
Djibouti-city 0.28472.2 0.0565.1 0.0384.9 0.05718 0.62532 0.1787 0.2571.34 0.03502.3 0.2539.7 This study
CSBQG, TEL 1760 77 204 57 423 195 MacDonald et al. (2000)

Site PAH concentration (ng/g dw) References

BaA Ch BbF BkF BaPy Per BghiPer IP PAH16

Hadhramout, Yemen 09.16 012.84 014.75 03.14 012.03 09.81 2.1199 Mostafa et al. (2009)
Suez Gulf-Egypt 6.1410.06 00.5 1.288.44 1.1212.32 02.17 0.1311.67 01.28 9.4945.52 Aly Salem et al. (2014)
Red Sea-Egypt 01409.9 01127.2 01012.6 01516 15.41456 01970.9 0833.1 15810,463 Nemr et al. (2005)
Abu Qir Bay, Egypt 0185 0297 0109 01390 Khairy et al. (2009)
Sardinia, Italy 0463 0364 0403 0*118 063.3 0250 Schintu et al. (2015)
Levantine Basin, Israel 1.13.2 0.93.3 1.45.5 0.91.7 0.82.8 1.23.9 1.14.4 11.848.3 Astrahan et al. (2017)
Djibouti-city 0.0339 0.1178 0.13348 016.3 0.1101.2 0.07103 0.168.75 2.653760 This study
CSBQG, TEL 108 166 150 1610 MacDonald et al. (2000)

6
M. Mahdi Ahmed et al.
Acknowledgements
The study was carried out with the nancial support from the
research fund granted to the CERD by the Presidency of the Republic of
Djibouti. We would like to thank Samaleh Ahmed Idriss and Leila Omar
Farah for performing the heavy metals and sediment characterization
analysis. Special thanks to Dr. Antoine Marie Caminiti for guiding us in
the right direction. We are thankful to Military Corps and particularly
the divers from the National Marine Corps lead by Col. Abdourahman
Cher for collecting samples under dicult weather conditions.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.marpolbul.2017.05.055.
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