Chemosphere 175 (2017) 505e513

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Occurrence of pharmaceuticals and personal care products in effluent-

dominated Saudi Arabian coastal waters of the Red Sea
Aasim M. Ali a, Helene Thorsen Rønning b, Walied Alarif a, Roland Kallenborn c, *,
Sultan S. Al-Lihaibi a, **
a
Department of Marine Chemistry, Faculty of Marine Sciences, King Abdulaziz University, PO. Box 80207, Jeddah 21589, Saudi Arabia
b
Faculty of Veterinary Medicine and Biosciences, Norwegian University of Life Sciences (NMBU), PO Box 8146 Dep, N-0033 Oslo, Norway
c
Faculty of Chemistry, Biotechnology and Food Science (KBM), Norwegian University of Life Sciences (NMBU), P.O. Box 5003, Christian M. Falsen veg 1, No-
1432 Ås, Norway

h i g h l i g h t s

PPCPs were analysed in seawater from coastal sites in Jeddah (Saudi Arabia).

High levels of PPCP (>10 microg/L SUM PPCPs) revealed sewage effluent contribution.

Even in background stations PPCPs were quantified.

A first pattern comparison identified diffusive sources influencing background locations.

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

Article history: The occurrence of selected pharmaceuticals and personal care products (PPCPs) and the pesticide
Received 4 December 2016 atrazine were investigated in seawater samples collected from stations located at effluent dominated
Received in revised form sites in the Saudi Arabian coastal waters of the Red Sea. PPCPs were analysed using solid phase extraction
17 February 2017
(SPE) followed by high performance liquid chromatography e tandem mass spectrometry (HPLC-MS/
Accepted 18 February 2017
Available online 20 February 2017
MS). A multi component method for the ultra-trace level quantification of 13 target PPCPs in Seawater
was developed and validated for the here performed study. The method procedure is described in detail
Handling Editor. Klaus Kümmerer in the supplementary material section. 26 samples from 7 distinct locations (2 directly influenced by
continuous sewage release) were chosen for the sampling of surface seawater. Based upon local sales
Keywords: information, 25 target substances (20 PPCPs, 4 pesticides and 1 stimulant) were chosen for the here
PPCPs reported method development. Thirteen PPCPs were detected and quantified in a total of 26 seawater
Pharmaceuticals samples. Metformin, diclofenac, acetaminophen, and caffeine were identified as the most abundant
Personal care products PPCPs, detected in maximum concentration higher than 3 mg/L (upper quantification limit for the here
Environmental pollutants
developed method). Concentrations were in the range of 7e >3000 (metformin), <LOQ e 2379 ng/L
Seawater
(acetaminophen) and 62e >3000 ng/L (caffeine). The contribution of direct sewage release on the PPCP
Red sea
LC-MS/MS levels detected was obvious, the target PPCPs were detected in the Al-Arbaeen and Al-Shabab coastal
Sewage release lagoons in high concentrations due to the low water exchange with the open sea and still ongoing
sewage releases in the lagoons. Also, substantial amounts of antibiotics were detected in all samples.
Levels and distribution profile of the detected PPCPs revealed high level release rates and give raise to
concern on potential environmental risks associated with the here document long term exposure on the
fragile coastal marine environment of the region but particularly in the nearby protected coral reef
environment outside the harbour region of Jeddah.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction

Pharmaceuticals and personal care products (PPCPs) are today

* Corresponding author.
considered as high priority environmental pollutants (Daughton
** Corresponding author.
E-mail addresses: roland.kallenborn@nmbu.no (R. Kallenborn), sallihaibi@kau. and Ternes, 1999; Halling-Sørensen et al., 1998; Kümmerer, 2001).
edu.sa (S.S. Al-Lihaibi). These compounds are found in sewage (Batt et al., 2008; Ternes,

http://dx.doi.org/10.1016/j.chemosphere.2017.02.095
0045-6535/© 2017 Elsevier Ltd. All rights reserved.
506 A.M. Ali et al. / Chemosphere 175 (2017) 505e513
1998; Weigel et al., 2004), river water (Dai et al., 2015; Kolpin et al.,
2002; Tan et al., 2015), groundwater (Del Rosario et al., 2014; Sacher
et al., 2001), seawater (Weigel et al., 2001, 2004), and even drinking
water (Carmona et al., 2014; Qiao et al., 2011). PPCPs are introduced
into the environment through several routes but primarily by raw
and treated sewage (Daughton and Ternes, 1999). The removal ef-
ficiencies of many PPCPs by conventional wastewater treatment
processes are low (Kosma et al., 2014; Stasinakis et al., 2013). PPCPs
do not need to be persistent for exhibiting hazardous effects. Due
reported to high-volume continuous discharge into the receiving
aqueous environment (pseudo-persistence), a long term exposure
must be assumed (Daughton and Ternes, 1999).
PPCPs like benzodiazepines and UV- filter compounds were
reported to bioconcentrate in marine organisms (Chen et al., 2015;
Chu and Metcalfe, 2007; Gomez et al., 2012). Due to the biochem-
ical design of PPCPs, a highly sensitive toxic response in the
exposed organisms must be assumed for most of the target sub-
stances at environmentally relevant concentrations (Cortez et al.,
2012; Gagne
et al., 2006; Giltrow et al., 2009; Martin-Diaz et al.,
2009; Nassef et al., 2010). However, environmental concentrations
are usually far below the therapeutic effect concentrations for the
respective PPCPs (Kummerer, 2001; Kolpin et al., 2002.
Therefore, sensitive analytical methods are required for inves-
tigating the occurrence and fate of these trace contaminants in
seawater. Since PPCPs occur usually at ultra-low level concentration
(ppq-ppt) in seawater, effective preconcentration in combination
with highly sensitive detection methods (HPLC-MS is a prerequisite
for the quantitative trace analysis of PPCPs in environmental
samples (Arpin-Pont et al., 2016).
Due to country specific prescription regulations, water treat-
ment and consumption profiles, the release and distribution
pathways for PCCPs are characteristic for the respective nations and
cannot be assessed sufficiently by extrapolation of earlier studies
and other countries evaluations (Pal et al., 2010). Therefore, a
country specific environmental assessment on the occurrence of
PPCPs in the Saudi Arabian environment is required as proper basis
for regulatory measures.
The Red Sea has a unique environment with relatively high
surface water temperatures (22e34  C) and salinity (36.5e41‰)
due to its location in an arid region and limited water exchange
with to the Indian Ocean (Rasul and Stewart, 2015). This unique
marine environment is the basis for a unique ecosystem with high
abundance of marine organism including coral reef, marine fish and
mammals species. Saudi Arabia, situated on the coast of the eastern
Red Sea.
Within Saudi Arabia, only 37% of the total wastewater produced
is treated in sewage treatment plants (STP) (Qadir et al., 2010)
though a target of achieving 100% sewage coverage by 2025 has
been set for all cities with populations greater than 5000 in-
habitants (KICP, 2012). Expecting a significant increase of Waste-
water production in the coming years, water reuse is being
considered to augment the water resources in addition to
groundwater supplies within Saudi Arabia and other Middle
Eastern and North African (MENA) countries (Drewes et al., 2012;
Hamoda, 2004). Water reuse was increased from 123 million m3/
year in 2006 to 219 million m3/year in 2010 in Saudi Arabia (Al-
Jassim et al., 2015). Within Saudi Arabia, there are at least thirty
major sewage treatment facilities (Drewes et al., 2012), the majority
of them apply secondary treatment procedure (Al-Jassim et al.,
2015).
The coastal city of Jeddah is currently the second largest city in
Saudi Arabia with a current population of 4 million inhabitants. The
coastline around this major city has been extensively affected by
development (Ziegler et al., 2016). The current wastewater treat-
ments facilities in Jeddah are currently charged over their
recommended capacities and are, thus, insufficiently treating the
receiving sewage (Ziegler et al., 2016). As a consequence, this
overflow leads to extensive discharge of raw or partially-treated
sewage into the coastal waters (Mudarris and Turkey, 2006). The
above described ineffective direct sewage dumping in the coastal
water of the Jeddah area has increased notably since 2002 after
sewage disposal in the artificial sewage lagoons east of Jeddah was
terminated, this caused important environmental problems (El
Sayed et al., 2015).
Generally, very little is known about the occurrence and fate of
anthropogenic pollutants in the waters off the Saudi Arabian coast.
However, a recently published survey on the occurrence of organic
environmental pollutant of emerging concern in effluent samples
from Saudi Arabian waste water treatment facilities revealed po-
tential continuous emission of PPCPs into the coastal Red sea
(Alidina et al., 2014). Effluent concentrations in ng/L to mg/L range
were detection for the target substances. Based upon these findings
the here reported study was conducted to investigate the occur-
rence fate of priority PPCPs in the receiving coastal sea water of the
Red Sea.
To our best knowledge, no scientific study is reported in the
literature on the occurrence of PPCPs in the Saudi Red Sea coastal
waters except the above-mentioned study on levels in direct ef-
fluences from Saudi Arabian wastewater treatment plants (Alidina
et al., 2014.
Thus, an investigation of the occurrence of PPCPs in effluent-
dominated coastal sea waters of the Red Sea is expected to add
urgently needed scientific information for adequate national
environmental assessments required for future regulative mea-
sures. This study aims at assisting in the assessment of new tech-
nological approaches for the replacement of the current outdated
wastewater treatment technologies. Furthermore, the here pre-
sented data represent the first scientific evidence on the occurrence
of PPCPs in the Red Sea Saudi Arabian surface coastal water.
2. Materials and methods
The quantification method was adjusted to the requirements of
surface water analysis in Red Sea seawater. The details on the
analytical method including Chemicals, equipment and procedures
can be found in the Supplementary materials section.
2.1. Selection of analytes
The target analytes in this study were selected based on their
previous detection in sewage effluent samples collected from Saudi
Arabia (Alidina et al., 2014; Shraim et al., 2017). The 20 original
target compounds in this study included:: i) pharmaceuticals:
acetaminophen (ACE), amitriptyline (AMT), atenolol (ATN), carba-
mazepine (CBZ), ranitidine (RAN), chlorpheniramine maleate
(CPN), metronidazole (MTD), sulfamethoxazole (SMX), trimetho-
prim (TMP), diclofenac (DCF), Warfarin (WAR), ciprofloxacin (CIP),
captopril (CAP), simvastatin (SIV), fluoxetine (FLX), metformin
(MET), cephalexin (CEP); ii), caffeine (CAF), iii) personal care
products: methylparaben (MEP), triclosan (TRC); iv) pesticides:
atrazine (ATZ), benzophenone (BEP), triclocarban (TRB); and N,N-
diethyl-meta-toluamid (DEET). Four isotopically labelled com-
pounds used as internal standards were included: acetaminophen-
(ring-d4), atenolol-d7, ciprofloxacin-d8, and atrazine-d5. The
complete information on the standards applied for the here re-
ported study can be found in Table S1 (supplementary materials
section).
 A.M. Ali et al. / Chemosphere 175 (2017) 505e513 507

2.2. Study area
Three main effluent-dominated regions (divided in seven sam-
pling sites and 26 sample locations) situated in the vicinity of
Jeddah were selected in this study; the effluent lagoons at Al-
Shabab (Sha 1e4 in Fig. 1) and Al-Arbaeen Arba 1e13 in Fig. 1).
Al-Shabab and Al-Arbaeen are two coastal lagoons connected with
the Red Sea via a 500 m wide channels.
Since the 1970s, both lagoons receive more than 100,000 m3
daily of partially treated sewage (El-Rayis and Moammar, 1998).
This is the main reason for the characterised estuarine circulation
pattern in these lagoons; steep surface salinity gradient of salinities
reaching about 5‰ close to the sewage effluents. During spring and
summer (March to the end of October), the water bodies of the two
lagoons are separated from the incoming water of the Red Sea
below a 2 m threshold (sill). Therefore, both the salinity and vertical
temperature profile of the receiving water in the lagoons are
developing differently compared to the coastal water outside the
lagoon (Al-Farawati, 2010; Pena-Garcia et al., 2014; Turki, 2016). A
relative stable salinity gradient with high water temperature are
usually observed. During late fall and winter, however, both lagoons
exhibit a flushing state where excessive Red Sea water inflow
flushes out the accumulated water masses from the lagoons
resulting in effective dilution and disappearance of the previously
stable vertical seasonal salinity gradient in the lagoon waters. Prior
to the here described sampling program, these sites were already
known as locations with significant high nutrients (Al-Farawati,
2010; El Sayed, 2002; Pen ~ a-García et al., 2014), heavy metals
(Basaham, 1998), and hydrocarbons levels in their surface waters
(Turki, 2016). In 2002 the municipality of Jeddah officially stopped
sewage dumping into the two lagoons and implemented a reha-
bilitation program for their waters, involving removal of accumu-
lated sludge and aeration of the water bodies using a numbers of air
pumps (El Sayed et al., 2015). However, recent field observation
confirms that there is still continuous sewage release ongoing in
the Al-Arbaeen lagoon.
Al-Kumrah (KM 1e4 in Fig. 1), the third site is located at the
South of Jeddah, receive about 300,000 m3 of partially treated
sewage daily (Basaham et al., 2009). In addition to the increasing
influence of human activities, sewage effluents from Al-Kumrah
includes a partially-treated sewage from many industrial in-
stallations (Abu-Zied et al., 2016). Al-Nawras (NAW 1e2 in Fig. 1) is
located near the heavily developed Jeddah Corniche. Obhur (Ob
1e2 in Fig. 1), Al-Mangrove and Al-Shuraa (Shura) sites were

Fig. 1. Map shows the selected sampling sites along the Saudi Arabian coast; stations 13 stations are located at Al-Arbaeen lagoon, 4 stations are located at Al-Shabab lagoon, 4
stations are located at Al Kumrah, Al Nawras, Obhur, Al Mangarove and Al Shraa (The maps are kindly provided by Google maps).
508 A.M. Ali et al. / Chemosphere 175 (2017) 505e513
considered as less contaminated locations.
2.3. Sampling protocol
Surface seawater samples were collected from all sites in 500 mL
amber glass bottles during March and May 2016. At Al-Arbaeen and
Al Shabab, seawater samples were collected aboard a small boat
using a 5-L Niskin sampler at 0.5 m sampling depth. Samples
collected from the coast of these lagoons and other sites were
collected from the surface (zero m depth). Samples were kept
cooled during sampling and stored at 4 ᵒC until sample prepara-
tion (for details, see Supplementary Information section). All
samples were preserved by adding ascorbic acidic (Fig. 1). In
addition, the sample preparation and solid phase extraction (SPE)
was performed not later than 4 days after sample collection to
prevent potential microbial transformation of the target PPCPs. The
general work flow for the sample preparation and quantification
with HPLC/MS is described in Fig. 2.
2.4. Multivariate data analysis
For the statistical treatment of the obtained data, multivariate
data analysis was performed to identify characteristic pattern dis-
tribution in PPCP concentrations among the selected sampling sites
using principal components analysis (PCA). PCA provides multi-
variate statistical information of the entire data which allows the
determination of pattern profiles by calculating the statistical dis-
tribution related to the two most relevant principal descriptors
(principal components 1 and 2). This method allows pattern
grouping and trend analysis (Saccenti et al., 2014). For our study
Pearson based PCA on not normalised data was performed using
XLS Stat software (Version 19.01, Addinsoft, Paris, F).
2.5. Method validation and quality control
A multi-component method (see supplementary material) was
developed for the quantitative determination of selected emerging
pollutants (PPCPs, a stimulant and pesticides) in seawater samples.
Fig. 2. General work flow of the sample preparation for quantitative analysis with
HPLC/MS.
A previously published method by Batt et al. (2008) (Batt et al.,
2008) was adopted to the need of the here performed study. All
compounds were separated in single chromatographic runs within
a total analysis time of 15 min (HPLC/MSxMS quantification). MDL,
ILOD and ILOQ values are summarised in Table S4. Instrument
detection limits ranged from 0.04 to 17.5 ng/L. The resulting
method detection limit (MDL) ranged from 0.08 to 26.7 ng/L. Except
for acetaminophen, the MDLs of all other target substances were
considerably lower than those reported by Batt et al., (2008). It is
worth mentioning that some compounds could not be retrieved
from the MCX cartridges (i.e., ciprofloxacin, captopril, simvastatin
and cephalexin). An earlier study (Batt et al., 2008) reported similar
behaviours for ciprofloxacin and metformin. Thus, the above-
mentioned substances were excluded from further validation and
quantification. Also, due to low instrument sensitivity for triclosan,
triclocarban, and benzophenone, these compounds were excluded
from further validation and quantification. Finally, all compounds
with recoveries in the range from 30% to 130% (at 500 ng/L) were
chosen for quantification in the available seawater samples
(Table S4). Significantly deviating recoveries at 3000 ng/L (linearity
range limit) may indicate saturation of the mass selective detector
(Table S4). After comprehensive quality control, 13 PPCP com-
pounds could be quantified an (out of original 25 chosen PPCPs). All
final target substances satisfying the recovery and calibration
criteria of the method are listed in Table 1.
Either ion suppression or signal enhancement may occur, when
analysed by LC-MS or LC-MS/MS in Electro spray ionisation (ESI) in
negative or positive mode (Cahill et al., 2004; Petrovi
c et al., 2005).
Matrix matched calibration curves were, therefore, applied in order
to compensate and detect possible matrix effects during method
validation. As shown in Table S5, metformin, metronidazole,
caffeine, sulfamethoxazole, and simvastatin express significant
matrix suppression effect as indicated by their respective slope of
the matrix matched calibration curve compared to the slope of the
solvent based calibration curve ratio (Sm/Ss) below 1. Seawater
matrix, however, causes signal enhancement (Sm/Ss > 1) for
atenolol, acetaminophen, amitriptyline, DEET, diclofenac, and
ibuprofen. For ranitidine, trimethoprim, chlorphenamine, carba-
mazepine, and methylparaben no significant matrix effect was
identified. Isotope-labelled compounds were used as internal
standards to account for losses during the sample preparation and
for concentration calculations.
Very low recovery rate (Table 2), for Aceminophen-d4 (12e20%)
were found. Therefore Aceminophene-d4 was finally excluded for
quantification. Finally, two isotope labelled internal standards
(ISTD) and one isotope labelled recovery standard (RecSTD) were
accepted and used for target substance quantification (see
Table 1
Final target compounds for quantification in seawater samples for the here pre-
sented study.
Compounds Abbreviation CAS number
Acetaminophen ACE 103-90-2
Atenolol ATN 29,122-68-7
Caffeine CAF 58-08-2
Carbamazepine CBZ 298-46-4
Chlorphenamine CPN 113-92-8
Diclofenac DCF 15,307-86-5
Ibuprofen IBP 1568-27-1
Metformin MET 657-24-9
Metronidazole MTD 443-48-1
N,N-diethyl-m-toluamid DEET 134-62-3
Ranitidine RAN 66,357-35-5
Sulfamethoxazole SMX 723-46-6
Trimethoprim TMP 738-70-5
 A.M. Ali et al. / Chemosphere 175 (2017) 505e513 509

Table 2
Relative Internal standards recovery rates [%] at 500 ng/L and 3000 ng/L spiked concentration in sea water calculated against the recovery standard Atrazin-d5 (100 ng/L).
Abbreviations: Atenolol-d7 (ATN-d7); R 1e7 e replicates (analysed in triplicate), SD e standard deviation.

Spiked seawater sample (500 ng/L) ATN-d7 Recovery ± SD [%] Spiked seawater sample (3000 ng/L) ATN-d7 Recovery ± SD [%]

R 1 69.9 ± 0.01 R 1 70 ± 2
R 2 68 ± 1 R 2 73 ± 2
R 3 68.8 ± 0.8 R 3 81.6 ± 0.1
R 4 59.4 ± 0.8 R 4 74.4 ± 0.2
R 5 62 ± 1 R 5 83.8 ± 0.6
R 6 61 ± 1 R 6 91 ± 1
R 7 67.6 ± 0.5 R 7 83.8 ± 0.2

Table S2). Efficiency tests for of ISTD recovery using Atrazine-d5 as lagoon with the maximum sum PPCP level well above 10 mg/L
recovery standard revealed considerable variations (see Table 2). (Table S1 and Fig. 2: Arba 2, 3 & 13). The Al-Arbaeen lagoon is
Based on this evaluation. Atenolol-d7 was chosen as suitable in- considered the most polluted sampling site with regard to PPCPs
ternal standard for recovery calculations (against Atrazine-d5) compared with all 7 locations investigated in this study. However,
based upon the here applied quality control protocol (Table 2). as already mentioned earlier, this is not a surprising result since the
The sample specific recovery rates were only considered as quality area is still used as sewage reservoir and only minor sewage
criteria and not used for recalculation of concentration values. treatment is expected (see introduction). Sum PPCPs concentra-
tions determined in the 13 samples of the Al-Arbaeen site vary
between 1.2 and 14 mg/L (Fig. 3). The here reported PPCP levels are
3. Results and discussion comparable with single compound concentrations reported in
freshwater effluents from the densest populated areas in the
3.1. Pharmaceuticals and personal care products (PPCPs), pesticides western world (Halling-Sorensen et al., 1998; Heberer, 2002; Jux
and caffeine in the Red Sea seawater et al., 2002; Boyd et al., 2003; Oulton et al., 2010; Fatta-Kassinos
et al., 2011; Fang et al., 2012). All individual compounds were
The above described validated method was used for the trace quantified in the determined instrumental linearity range from the
level quantification of selected PPCPs in effluent-dominated Saudi individual ILOD (see Table S4). For individual compounds with
Arabian coastal waters of the Red Sea near Jeddah. Since all concentration values exceeding 3000 ng/L were included for
seawater samples were filtered before extraction, the reported pattern profiling and sum PPCP calculations. However, for these
concentrations represent the soluble fraction of the detected target samples the final sum concentration may be even underestimated
PPCPs only. Thirteen compounds were detected in most seawater and therefore considerated as indicative only.
samples with concentrations ranging from below ILOQ to concen- The location specific relative compound distribution profiles are
trations greater than 3000 ng/L (Table 2 and Table 3). All concen- summarised in Fig. S1 (A-G, supplementary material section). The
tration >3000 ng/L exceeded the confirmed linear range of the compounds of high detection frequency (f) were: caffeine
instrumental method and, thus, should be considered as semi- (f ¼ 100%), acetaminophen (f ¼ 100%), DEET (f ¼ 100%), sulfa-
quantitative according to the here applied quality control guide- methoxazole (f ¼ 100%), ibuprofen (f ¼ 100%), metronidazole
lines (, saturation of the detector may affect the instrument sensi- (f ¼ 92%), carbamazepine (f ¼ 92%), chlorpheniramine (f ¼ % 92),
tivity; see supplementary material section). trimethoprim (f ¼ 77%), ranitidine (f ¼ 81%), diclofenac (f ¼ 65%),
From the original list of target substances (n ¼ 25, see Table S1), atenolol (f ¼ 73%), and metformin (f ¼ 85%). Amitriptyline and
13 compounds could be quantified in the seawater samples (n ¼ 26) Atrazine were detected with concentrations below the ILOQ in
spread over 7 sampling locations (Fig. 1). All substances were found most stations. Cephalexin was detected in Obhur only at a con-
in at least 65% of all samples analysed. Eight compounds (8) were centration of < LOQ. Ciprofloxacin was also detected in only one
detected and quantified in more the 90% of the samples (Table 3) station (Al-Arbaeen) at a concentration of < LOQ. A broad range of
representing the core PPCP substance group of the here presented maximum PPCPs concentrations reported in this study, i.e. < ILOQ
study (MTD, ACE, CAF, SMX, CBZ, CPN, DEET, IBP). to >3000 ng/L. Metformin, caffeine, and diclofenac occurred in the
The highest PPCP concentrations were found in surface water Al-Arbaeen lagoon at > 3000 ng/L. Concentrations above 3000 ng/L
samples close to the sewage outlet at the inner part of Al-Arbaeen are reported and discussed but may be even underestimated due to
saturation in the mass selective detector. In addition to the national
Table 3 prescription rate and application procedures, the relative pattern
Detection frequency of all quantified PPCPs (for abbreviations of compound names, distributions shown for the seven sampling sites in Fig. 4(AeG)
see Table S1). seem to be a combined result of aging (temporal and spatial dis-
Compounds Samples [n] Detection frequency Relative abundance tance to potential emitting sources), transformation pathways
(photochemical and microbial) as well as environmental stability
MET 26 22 85
ATN 26 19 73
(persistence). The source near locations (i.e., Al Arbaeen, Al-Shabab
RAN 26 21 81 and Al Kumrah), characterised by a recent high-volume continuous
MTD 26 24 92 supply from STP emission of the here analysed PPCPs, are domi-
ACE 26 26 100 nated by Aceminophene and Caffeine as shown for the Al-Arbaeen
CAF 26 26 100
(3 and 48% respectively) and Al-Shabab (10% and 53%, respectively)
SMX 26 26 100
TMP 26 20 77 lagoons.
CBZ 26 24 92 The stimulant caffeine is today considered as a chemical indi-
CPN 26 24 92 cator of anthropogenic influence on aqueous environments and
DEET 26 26 100 clearly demonstrate here also the polluting effect of the nearby
DCF 26 17 65
IBP 26 26 100
community on the examined marine coastal environments. It is
510 A.M. Ali et al. / Chemosphere 175 (2017) 505e513

Fig. 3. Average PPCP Sum concentration in surface seawater samples from all locations in the vicinity of Jeddah. Abbreviations: Arba ¼ Al Arbaeen, Shab: Al Shabab, KM: Al Kumrah,
NAW: Al Nawras, Ob: Obhur, Man, Al Mangarove, Shra: AL Shraah (for locations, see Fig. 1).

Fig. 4. Relative PPCP distribution profiles for the respective sampling locations (AeG).

assumed that caffeine stems mainly from domestic households, reflects the local consumption profile of caffeine-containing bev-
restaurants, and public locations. However, caffeine is usually erages, excreted and exposed to the local sewage treatment pro-
readily retained in modern sewage treatment plants (STP) and cedures before released into the STP effluent. Due to the high levels
 A.M. Ali et al. / Chemosphere 175 (2017) 505e513
identified here, less advanced sewage treatment procedures must
be assumed for the Jeddah STPs. A follow up on potential sources
and control of the here applied STP procedure is urgently
recommended.
In Al Arbaeen, Diclofenac, Metformin and Caffeine represent
roughly 92% of the quantified 13 PPCPs, whereas Caffeine, Acet-
aminophen and Metformin stand for ca. 90% of the total PPCPs
quantified in the Al-Shabab samples. However, since Diclofenac and
Acetaminophen are both non-Steroid Anti-inflammatory drugs
(NSAID) and available as over the counter drugs also in Saudi
Arabia, mainly domestic sources must be assumed for the PPCP
release for both sites and user specific application variations may
cause the here observed differences (Figs. 3 and 4). A more diverse
picture is reflected in the pattern profiles for the background sites
(i.e. Obhur, Al-Mangrove). In the background location Obhur,
however, Metronidazole (MTD, 17e30 ng/L) and Sulfamethoxazole,
(31e36 ng/L) both potent antibacterial agent are the predominance
PPCPs in surface seawater at high concentrations (>70% Sum
PPCPs).
All concentrations are summarised in Table S6. The highest
quantified concentration was found for diclofenac (10,221 ng/L) at
Al-Arbaeen (ARB-3). The highest quantified concentration of
caffeine was 7708 ng/L at Al-Arbaeen (ARB-13). Metformin fol-
lowed as the third highest PPCP with concentrations up to 4801 ng/
L these three compounds are identified as the predominant (See
Table S6). The highest quantified concentration of acetaminophen
was 1234 and 2346 ng/L at Al-Arbaeen and Al-Shabab lagoon
respectively. The NSAID ibuprofen was also found in elevated
concentrations (284, 660, and 127 ng/L at Al Arbaeen, Al-Shabab
lagoon, and Al Kumra, respectively). NSAIDs are, thus, found to
contribute in high concentration to the overall PPCP levels reported
(ca 20 ± 5% of the sum PPCPs in the ARB samples). The here re-
ported PPCP levels found in Al-Arbaeen and Al-Shabab are most
probably caused by the recent continuous discharge of only
partially treated sewage in these lagoons (see release pattern
described in the introductory section). It should be noted that the
here analysed samples were collected in the period between late
March and Mid May. As mentioned earlier, during this time of the
year, there is no mixing between the water masses of the two la-
goons and the open sea.
For a more in-depth pattern analysis, a Principal component
analysis (PCA) of the entire data set was performed. PCA was
Fig. 5. PCA bi-plot (observations and variables) for the target PPCPs in the selected sample locations.
511
performed on unmodified data from all sampling sites (7 locations,
Fig. 1). The two major principal components (F1 þF2) explain
around 89% of the observed variations (Fig. 5). This PCA based
statistical pattern evaluation confirms characteristic site-specific
pattern profiles for the PPCPs investigated, The PPCP levels in the
two lagoons Al-Arbaeen (Arb1-13) and Al-Shabab (Shab1-2) are
elevated, as previously mentioned. Locations like Al-Kumrah, Al
Nawras, Obhur, Al Shraa, and Al Mangrove are less contaminated
(for sample info see Fig. 1 and Table S6). The PCA bi plot depicted in
Fig. 5 shows that diclofenac (DCF), metronidazole (MTD), caffeine
(CA) and Metformin (MET) are the main divers for the PPCP pat-
terns. The Al-Arbaeen lagoon, identified as contaminated location,
is characterised by elevated Metformin (MET) levels. However, due
to the additional, strong contribution of caffeine to the profiles of
the contaminated sites (Al Arbaeen and Al-Shabab) mainly do-
mestic sources are identified as source for the here identified PPCP
pollution.
However, also here short-term variations in the emission pro-
files of the respective samples account for a considerable spreading
of the variable plot (samples) in the PCA biplot (Fig. 5). Even within
the Al-Arbaeen subset of surface water (n ¼ 13, Fig. 3), concentra-
tion variations over 2 orders of magnitude are observed (Table S6,
Sum PPCP: 2424e14,020 ng/L). The low contaminated locations
(Obhur, Al- Magarove, Al-Kumrah) are characterised by stronger
influence of Metronidazole (MTD) and Ibuprofen (IBP.
Based on salinity calculation, a recent published investigation
(El Sayed et al., 2015) estimated that the Al-Arbaeen surface mixed
layer constituted of 88.2% of seawater, compared to 94.7% of
seawater in the Al-Shabab surface mixed layer. This independent
finding indicates that the current wastewater release in the Al-
Arbaeen lagoon is higher compared to the Al-Shabab waters. For
station Arba 13 (Al Arbaeen), the highest level of Sum PPCPs in this
study is reported (Average sum PPCP ¼ 14,019 ng/L; Fig. 2), indi-
cating ongoing sewage release.
Al Kumra showed significantly lower PPCP concentrations
(compared to Al Arbaeen) although it is known as sewage influ-
enced location. However, the considerably lower concentrations
may be the consequence of continuous effective dilution with
coastal seawater (in contrast to the Al-Arbaeen site), since this
location is directly connected to the open Red Sea. As expected,
PPCPs occur in Nawras, Obhur, Al-Shuraa, and Al-Mangrove at a
lower level concentration (Sum PPCPs of several hundred ng/L).
512 A.M. Ali et al. / Chemosphere 175 (2017) 505e513

Table 4
Comparison of selected maximum concentrations reported in international studies on PPCP burden in surface- and waste water samples.

Compounds Asia Europe America

KSA, China KSAa KSAb Taiwan Hong Vietnam UK Belgium Germany USA
Red Kong
Sea

SMX 63 134a 730 ND 47 Nd 96 480 e 3.4 g

DCF 14,020 32.7 1260 53.6 195 ND 6.2 f 0.6 g
IBP 508 31.1 930 57.1 755 0.6 f 30 g
CBZ 110 25.5 1200 3.83 23 321 0.9 g
ACE 2363 99,600 16.7 ND 11 g
f
CAF 7708 16,500 16.9 15 44.7 h
ATZ 2.2 30
DEET 49 415
MET 4801 31,200
Ref. This Xu et al. 2007; Alidina Shraim Jiang et al., 2014; Minh Manaki Thomas Wille Hirsch et al., 1999; Vidal-Dorsch et al.,
study Zhao et al., 2010 et al., et al., Fang et al., 2012 et al., et al., et al., et al., Weigel etal. 2002 2012; del Rey et al.,
2014 2017 2009 2007 2004 2010 2012
a
KSA: Kingdom of Saudi Arabia, WWTPs effluents.
b
KSA: Kingdom of Saudi Arabia, raw wastewater samples.

However, the detection of antibacterial PPCPs (i.e. Trimethoprim,
Sulfamethoxazole, Metronidazole) in ppb concentrations and MTD
even identified as the predominant compound among the analysed
PPCPs indicate different sources and warrant further investigations.
4. Perspectives
completed. The NMBU Department of Food Safety and Infection
Biology (MatInf) allowed access to their analytical laboratories. The
King Abdulaziz University (Jeddah, Saudi Arabia) funded the
research stay of Aasim M. Ali at NMBU in 2016. Parts of the
analytical work was supported by internal funding of the NMBU
Faculty of Chemistry, Biotechnology and Food Sciences (KBM).

The here reported study on the presence and distribution profile
of selected PPCPs revealed high levels of PPCP residues with
maximum levels of >10 mg/L SUM PPCPs in surface seawater close
to the identified point sources (STP effluent). Compared to a se-
lection other studies on the occurrence of PPCPs in surface water,
the here measured levels are in the upper range and well compa-
rable with concentration found in western European and Asian
samples (Table 4). Diclofenac reported in this study was the highest
value reported in surface waters, even exceeding the effluent levels
reported in a comparison of sewage treatment plant effluents in
Saudi Arabia (Alidina et al., 2014). Ibuprofen (IBP) was found in
comparable levels as shown in KSA effluent study (Alidina et al.,
2014) and in the UK Thomas et al., 2004) For aceminophen a
clear dilution effect is reported here compared to the Saudi Arabia
(KSA) effluent studies (Alidina et al., 2014).
Even at the selected rural background sites, supposedly less
influenced by direct PPCP release, elevated concentrations were
found in surface water samples in the range of several hundred ng/L
(Sum PPCP 178e351 ng/L). These findings indicate that only
incomplete dilution of the PPCP burden is taking place along the
passage into the open Red Sea, at least for the high contaminated
sites (Al-Arbaeen and Al-Shabab). Furthermore, antibacterial
agents were quantified as the predominant PPCPs in low contam-
inated locations like Al Nawras, Obhur, Al-Shuraa and Al-Mangrove
(Trimethoprim at Obhur 6 ng/mL; metronidazole: 54.7 ng/L;
Maximum concentration compared to Al Shabab: Trimethoprim:
Average 65 ng/mL; Metronidazole: Average 60.77 ng/L). These
concentrations are similar compared to those found in the high
contaminated locations (Al-Arbaeen and Al-Shabab). Thus,
continuous low-level exposure to the local microbial communities
cannot be excluded and should, thus, be investigate in follow-up
studies.
Acknowledgements
Without the help and support of many colleagues and experts at
our respective institutions, the here reported study could not be
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.chemosphere.2017.02.095.
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