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Marine Pollution Bulletin xxx (xxxx) xxxxxx

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Marine Pollution Bulletin


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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 important class of persistent organic pollutants in the marine environ-
inorganic contaminants is a major concern (Islam and Tanaka, 2004). ments, particularly in estuaries, harbors and shallow coastal areas
Red sea appears to suer from high anthropogenic pressure due to exposed to anthropogenic inputs e.g. a renery site (Barakat et al.,
inputs from industrial, sewage euents, shipping activities, spillage 2011; Baumard et al., 1998; Ne, 1985; Nemr et al., 2005; Syakti et al.,
coastal activities and natural seeps (Dou Abul et al., 1998; Khalaf and 2013). Anthropogenic sources of PAHs in the marine environment are
Kochzius, 2002; Kress et al., 1999; Nemr et al., 2005; Walker and generated through incomplete combustion (e.g. coal, petroleum and
Ormond, 1982). It leads to contamination of the surrounding area not wood) or derived from crude and rened petroleum products (oil spills,
only by organic compounds (e.g. polycyclic aromatic hydrocarbons, routine tankers operations, oil exploitation, etc.). PAHs hazardous
PAHs) but also to heavy metals such as Cr, Ni, Cu, Zn, As and Pb property, lipophilicity, low water solubility and adsorption to marine
(Fiedler et al., 2009; Ugochukwu and Leton, 2004). Furthermore coastal particles and sediments make them a group of chemicals that may aect
sediments act as temporary or long-term sink and is one of the most wildlife and humans via the food chain which prompted US EPA to
important reservoirs of environmental pollutants. include 16 PAHs within the priority pollutants list (Manoli et al., 2000).
Heavy metals occur naturally in the ecosystem at various levels of PAHs are known to have adverse eects on humans and the environ-
concentrations. Some heavy metals are essential for biological function ment through mechanism of carcinogenesis (IARC, 2010) as well as
in trace concentrations such as Cu, Cr, Mn, Zn and Co while high acute and developmental toxicity has been observed in the aquatic
concentrations of essential element have adverse eects on living environment (Ne, 1985).
organism (Hogan, 2010). Metals bioaccumulating in the food chain Several data is available from Yemen, Egypt, Sudan and Saudi
pose a risk to human exposure and damage to predators (Amundsen Arabia (Al-Shwa, 2003; Aly Salem et al., 2014; Ashraf and Salam,
et al., 1997; El-Moselhy et al., 2014; Muchuweti et al., 2006). 2012; Barakat et al., 2011; Bejarano and Michel, 2010; Dou Abul et al.,
On the other hand polycyclic aromatic hydrocarbons (PAHs) are an 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 organic solvents used for the analysis n-hexane, dichloromethane and
knowledge this area has never been investigated in detail for organic acetone were of HPLC grade (Sigma Aldrich). Mixture standards (PAH
contaminants and heavy metals both occurring naturally and anthro- Mix, EPA), individual surrogate and internal standards (phenanthrene-
pogenically, which may enter into the marine ecosystem from various d10, pyrene-d10, chrysene-d12) were obtained from Sigma Aldrich for
point sources. identication and quantication of PAHs. Dichloromethane, n-pentane,
The present study is the rst investigation of the current status of n-hexane, (VWR, France) for PAH extraction and clean-up were of HPLC
PAHs and heavy metal concentration in surface sediments of Djibouti- grade. Silica gel-60 (200300 mesh), alumina (200300 mesh) and
city coastal area. The results provide a valuable reference data set for copper powder (> 230 mesh) were purchased from VWR
environmental managers. International (France). Certied Reference Material NIST 1941b
Djibouti city is located at 1130N, 4300E in the Horn of Africa, PAHs, PCBs and pesticides on Fresh Water Sediment and IAEA-158
Fig. 1. shows the general outline of the Republic of Djibouti. It has a were purchased from Sigma-Aldrich and International Atomic Energy
very hot and humid yet rainless summers (42 C and less 215 mm Agency respectively. All glassware for metal analysis was acid washed
annual precipitation) and warm winter season (21 C). The semi- while for PAH analysis was rinsed in dichloromethane followed by
enclosed nature of the Red Sea limits the opportunity for renewal of acetone to remove organic residues (Fig. 2).
the water mass. The coastline is composed of a mixture of eluvial and Metals extraction from sediment was performed according to
colluvial deposits, taluses, sheet oods, dunes and beach deposits with procedure described by ISO 11466. Briey, 3 g the dried sediment at
tidal range is 03 m relative to Chart Datum (Schlter, 2008). The 105 C was transferred to Kjeldahl tubes and was left overnight after the
monsoon wind vary from North-East during winter and South-West addition of 21 mL of hydrochloric acid and drop by drop addition of
during summer season. Increasing activity in the capital has caused oil 7 mL nitric acid solution followed by 15 mL of nitric acid. In a Kjeldahl
spills due to accident, chronic release of industrial contaminants mostly block, the suspension was reuxed for 2 h. After reux, the tube were
untreated. Furthermore untreated or insuciently treated wastewater let to reaching room temperature, the suspension was ltered using
is discharged into the sea. 0.45 m membrane while thoroughly rinsing the digestion tubes with
Surcial sediment samples (010 cm, n = 28) based on their 30 mL milliQ water (< 18 m/cm). The ltrate was quantitatively
dierent potential levels and sources of contamination used in this transferred to a 50 mL volumetric ask and analyzed.
study were collected in Djibouti-city from January to April 2016. The PAH's extraction was performed accelerated solvent extraction with
sampling time coincides with an intense activity of Ambouli Wadi (dry a Dionex ASE 200. A 33 mL extraction cell was packed with two
river) which renewed surface sediment in Djibouti bay. The landmarks cellulose lter, glass bers (pre-cleaned by heating at 450 C over night)
in the adjacent land areas to the sampling sites were recorded and all and the spiked sediment Briey 5 g of nely sediment previously sieved
sampling sites were dened using global positioning system (Table S1). at 2 mm were spiked with deuterated surrogate standards, Ph-d10 and
Twelve samples were collected in Djibouti-city bay, eleven stations Chr-d12. The extraction cell was left for 20 min to make sure of full
were collected in Djibouti-city mangrove and ve samples in the percolation through the sample. Extraction conditions were as follow:
recreational and tourism area. Sediments along the shore were collected 100% DCM was used as solvent and a temperature of 100 C. The heat
by foot while sediments from the bottom sea (250 m) were collected up time was 5 min and the program had ve static cycles with 2 min
using a diver with an adequate container and stored at 4 C during extraction time at a pressure of 1500 psi and a ush volume of 35%
transportation to the laboratory. Sediment samples were dried at 30 C (Tronczyski, 2005). The sediments samples were extracted in two vials
in a ventilated air drying oven and subsequently sieved to < 2 mm which were combined and pre-concentrated to < 5 mL under a gentle
and < 0.15 mm for polycyclic aromatic hydrocarbons (ISO stream of nitrogen. Sulfur interference was removed by shaking the
15527:2008) and heavy metal (ISO 11466:1995) determination respec- extract with copper powder previously activated with 10% HCl and
tively. washed ve times with dichloromethane and n-hexane. The extracts
High purity ICP selected heavy metals standard solution (1000 ppm) were evaporated to dryness and solvent exchanged to n-heptane in
was obtained from Horiba (Jobin Yvon, France). Hydrochloric and order to purify and fractionated on alumina:silica (1:1, w:w) column to
nitric acid (70%) were of analytical grade (Sigma-Aldrich). All the 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 factor and pollution load index were determined.
internal standards. Enrichment factor (EF) was applied to investigate the degree of
pH was measured after 1 h stirring of a soil:ultrapure water with a sediment metal contamination compared to background as well as to
1:5 ratio (NF ISO 10390, pH meter PC650, Eutech Instruments). dierentiate metal source originating from anthropogenic and natural
Sediment organic carbon is based on Walkley-Black chromic acid wet means (Ergin et al., 1991). It involves normalization of selected metals
oxidation method (Walkley and Black, 1934) and pipette method was with respect to a reference element such as Al, Fe and Mn (Karbassi
used for particle size distribution (Day, 1965). et al., 2008). Fe was used as a normalizer because it is rich in earth crust
Trace metals levels were measured by an inductively coupled and assuming that it is free of anthropogenic impact. The EF was
plasma atomic emission spectrometer (ICP-AES, Ultima 2 Horiba calculated using the following equation:
Jobin Yvon) after acid digestion. Blank samples were prepared and Me
treated exactly in the same way as the samples. Instrument calibration ( Fe ) sample
EF (Me) = Me
standards were prepared using mono-element certied reference solu- ( Fe ) Background (1)
tion (Merck). The DLs were in the range of 0.010.08 mg/kg for
Me
selected metals. Certied reference material IAEA-158 was used to where ( Fe ) sample represents the ratio of concentration of selected
Me
validate analysis and measured values average ranged between 80% metals to that of Fe in stations of study and ( Fe ) Background is the same
and 101% (Table S3). Analytical residual standard deviations on ratio of the background concentrations.
triplicate samples were between 2 and 6%. Contamination factor (CF) determines the level of sediment anthro-
PAHs analysis were conducted on a capillary gas chromatography pogenic metals contamination and calculated according to (Hakanson,
coupled with mass spectrometry (GCMS; Autosystem XL GC and 1980):
TurboMass from Perkin Elmer, USA) equipped with an Elite 5MS
(Me) sample
capillary column (Perkin Elmer, 30 m 0.25 mm 0.25 m lm CF (Me) =
(Me) Background (2)
thickness). Chromatographic conditions were as follows (Kanzari
et al., 2014): splitless injection (30 s) and PSS injector programmed where (Me)sample represents the concentration of selected metals in
from 50 C to 250 C for 1 min to reduce solvent peak with a constant samples and (Me)Background is the background value of that element.
ow of Helium at 1 mLmin 1. For PAH, the oven temperature was as The background levels used to calculate EF and CF were Fe
follows: from 40 C (held for 2 min) to 120 C (45 Cmin 1) to 310 C (47,200 mg/kg), Cr (90 mg/kg), Cu (45 mg/kg), Zn (95 mg/kg), Pb
(5 Cmin 1) and followed by an isothermal for 20 min at 310 C. (20 mg/kg), Co (90 mg/kg), Cd (0.3 mg/kg), Ni (68 mg/kg) reported
16 US EPA priority PAHs were quantied using surrogates (phenan- for sedimentary rocks were considered as background values (Turekian
threne-d10, m/z 188 and chrysene-d12, m/z 240) and internal standard and Wedepohl, 1961).
(pyrene-d10). All data were subject to procedural and matrix blanks. The pollution load index (PLI) is a tool that investigates the pollution
Procedural blanks were carried out between each batch of ve samples status of dierent samples in the study area using the following
and no contamination was observed. Matrix blanks were performed equation (Tomlinson et al., 1980):
following the same procedures used for samples. Individual mass of
PLI = (CF1 CF2 CF3 CFn )1 n (3)
each PAH in the blanks was insignicant relative to sediment samples.
The mean recoveries (%) for surrogates in the sediment samples were where n is the number of studied metals and CF is the calculated
84% to 102% for PAH. The relative standard deviation (RSD) for PAH contamination factor.
ranged between 0.9%4.6% and the detection limits of PAH with a Classication of EF, CF and PLI limits indicating low, moderate and
signal to noise ratio of 3 were 0.010.18 ngg 1 dw (Table S8) severe contamination were summarized in Table 1.
An overall assessment of sediment was used to evaluate the level of Diagnostic criteria used in the identication of PAH sources and
metal contamination from natural and anthropogenic sources in origin were Ant/(Ant + Phe), Fl/(Fl + Pyr), BaA/(BaA + Chry), IP/
Djibouti. Three approaches, (i) enrichment factor, (ii) contamination (IP + BghiP), BaA/Chry and IPyr/BghiP and summarized in Table 1.

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

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

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

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


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
Fig. 4. Diagnostic ratio plots of Fl/(Fl + Pyr) vs Ant/(Ant + Phen). 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
Seven stations ranged from 0.55 to 0.8 suggesting that PAHs originated the Red Sea. The concentrations of total 16 PAHs varied widely
from grass/wood and coal combustion. Most of those sites corresponds depending on the sample location and ranged from 2.65 to
to mangrove area which was burnt in the 8090s. Eight stations mostly 3760.11 ngg 1. More than 32% of the sites had a total content of
located in Djibouti-bay with a Fl/(Fl + Py) ratio < 0.4 indicating a PAHs > 200 ng/g which can be considered low to moderate pollution
petrogenic source of PAH. This area has been subjected to a petroleum PAHs. Sources of PAHs were determined by the molecular diagnostic
input since 1997 and is a major shipping thoroughfare. There is a huge ratio of Ant/(Ant + Ph) vs. Fl/(Fl + Pyr). Eight stations mostly located
number goods transporting and tourist boats which could explain the in Djibouti-bay with a Fl/(Fl + Py) ratio < 0.4 indicating a petrogenic
petrogenic source. source of PAH. There is a huge number goods transporting and tourist
The sediment quality guidelines are being used by various federal boats which could explain the petrogenic source.
and provincial agencies in North America in order to protect freshwater During our sampling period, Ambouli Wadi was running and hence
and marine ecosystems (Long and MacDonald, 1998; MacDonald et al., the low level of contaminant could come from the Wadi's water renewing
2000). Variables of quality for Sediment containing organisms were the upper layer sediment. However the present results provide baseline
classied into dierent categories: Threshold eects levels (TELs), information on the metal and PAH pollution in Djibouti city against
eect range low values (ERLs) probable eect levels (PELs) and eect which future anthropogenic eects could be assessed. A few hotspots
range median values (ERMs). Table 4 also lists the consensus based were identied, hence these sources are under investigation and the
sediment quality guidelines (CBSQG) values for selected polycyclic quality of sediment monitored. Furthermore, we recommend including
aromatic hydrocarbons as threshold eect concentration (TEL) nutrients that may cause eutrophication, n-alkanes, PCBs and pesticides
(MacDonald et al., 2000) and presents studies on PAHs in the Red sea in future monitoring programs. To the best of our knowledge, it is the
and Gulf of Aden. CBSQG values were exceeded by Naphthalene, rst study on Djibouti city, it could be used as a contribution to the
Fluorene, Phenanthrene, Anthracene, Chrysene and Benzo[a]anthra- 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. Marine Pollution Bulletin xxx (xxxx) xxxxxx

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