Hindawi

Journal of Analytical Methods in Chemistry

Volume 2017, Article ID 2629365, 13 pages
https://doi.org/10.1155/2017/2629365

Research Article
Petroleum Hydrocarbon Fingerprints of Water
and Sediment Samples of Buffalo River Estuary in
the Eastern Cape Province, South Africa

A. O. Adeniji,1,2 O. O. Okoh,1,2 and A. I. Okoh1,3

1
SAMRC Microbial Water Quality Monitoring Centre, University of Fort Hare, Alice 5700, South Africa
2
Department of Chemistry, University of Fort Hare, Alice 5700, South Africa
3
Applied and Environmental Microbiology Research Group, Department of Biochemistry and Microbiology,
University of Fort Hare, Alice 5700, South Africa

Correspondence should be addressed to A. O. Adeniji; adenijigoke@gmail.com

Received 9 February 2017; Revised 26 March 2017; Accepted 3 April 2017; Published 30 May 2017

Academic Editor: Paolo Montuori

Copyright © 2017 A. O. Adeniji et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Petroleum hydrocarbon status of the Buffalo River Estuary in East London, South Africa, was evaluated from January to May,
2016. Surface water and sediment samples were collected from five points in the estuary and extracted using standard methods.
The extracts were subsequently analyzed by gas chromatography-flame ionization detection. Results showed that total petroleum
hydrocarbon (TPH) varied from 7.65 to 477 𝜇g/L in the water and 12.59 to 1,100 mg/kg in the sediments, with mean values of
146.50 ± 27.96 𝜇g/L and 209.81 ± 63.82 mg/kg, respectively. Concentrations of TPH in the sediments correlated significantly with
organic carbon (OC) in both seasons. TPH and OC levels were slightly lower in summer than in autumn in the two environmental
matrices, and the average amount of TPH in the water samples collected from all the sampling stations was generally lower than
the EU standard limit of 300 𝜇g/L. However, the levels in the sediments exceeded the EGASPIN target value (50 mg/kg) for mineral
oil but were below the intervention value (5,000 mg/kg), indicating a serious impact of industrial growth and urbanization on the
area, although the n-alkane ratios and indexes used for source tracking revealed excessive flow from both natural and anthropogenic
sources.

1. Introduction as a potential reservoir of the petroleum hydrocarbons in the

marine environments, posing risk of bioaccumulation [4, 6].
The presence of chemical contaminants in the coastal envi- Assessment of the physicochemical properties of the
ronments from many anthropogenic sources is a major threat water and sediment is also very important because these
to the marine water [1, 2]. Large amounts of these con- quality parameters are capable of affecting the biological
taminants through sewage, petroleum spills, municipal and characteristics of the environmental matrices and are the
industrial discharges, and automobile wastes and vehicular basis for judging the suitability of such water body for its
emission due to incomplete combustion of fossil fuels are designated uses [10–12]. Although some of these parameters
possibly carried by river runoffs through their estuaries into may have limited health significance, international standards
the sea [3, 4]. Petroleum hydrocarbons are one of the major necessitate their determination [13]. The physicochemical
pollutants which are frequently discharged into the coastal characteristics of each n-alkane in water and sediment sam-
water, though not usually regulated as hazardous wastes [5, 6]. ples will therefore depend on the source of contamination in
Although they are naturally present in very low concentra- the environmental matrices [14].
tion in the marine sediments, larger amount comes from Some studies recently conducted on the physicochemical
petrogenic and pyrogenic sources [7–9] and bottom sediment parameters of different water bodies across the globe were
which is the habitat of many aquatic organisms is recognized reported. Among the qualities assessed are pH, dissolved
2 Journal of Analytical Methods in Chemistry

oxygen, temperature, turbidity, conductivity, total dissolved

solids, and total suspended solids [11, 15, 16]. Analysis of sed-
iments qualities has also been found very paramount being
a major site for organic matter decomposition. Continuous
accumulation of pollutants due to biological and geochemical
mechanisms can be toxic to the sediment dwelling organisms
and fish, resulting in decreased survival, reduced growth, or
impaired reproduction and lowered species diversity. Some
recent findings on quality parameters of sediment like pH,
electrical conductivity, moisture content, organic carbon, and
organic matter were also reported [17, 18].
Buffalo River Estuary is the mouth part of the long Figure 1: Map of Buffalo River Estuary, East London.
Buffalo River that covers about 1287 km2 area before draining
into the Indian Ocean in the coastal city of East London.
The river flows through some major towns (Bhisho, King
William’s Town, Zwelitsha, Mdantsane, and East London) Five (5) sampling locations on the Buffalo River Estuary
and industrial areas that cover almost 12% of its catchment were chosen on the basis of the level of anthropogenic pres-
area. Three major tributaries that feed the Buffalo River with sures (Table 1; Figure 1). Monthly sampling was undertaken
runoffs, raw sewage, solid wastes, and industrial effluents between January and May, 2016, mostly during the high tide
are the Mgqakwebe, Ngqokweni, and Yellowwoods rivers except in February, spanning through summer and autumn
mainly from densely populated urban and agricultural areas seasons. Duplicate water samples were collected 100 mm
of the province [19]. Surrounding the estuary are the East below the surface level from two points (about 5 m apart)
London harbour and other direct users like Sea Spirit Fish in each sampling location with precleaned 1 L amber bottles,
Market, Vukani Petroleum, BP South Africa, Mercedes Benz pooled together to obtain a representative sample [21]. They
South Africa, Chevron (Pty) Ltd., Engen, and Total South were acidified to pH < 2 using 6 M hydrochloric acid (HCl).
Africa among others. First and Second Creeks are instances of The sediment samples were however collected only from 4
influent rivers which contribute to the inflow of stormwater, locations using Van Veen Grab sampler, because the estuary
sewerage, and domestic and industrial runoffs into the substratum at E5 was rocky. All the samples were transported
estuary [20]. to the laboratory immediately on ice chest for analysis [22,
Previous environmental studies in the area focused on 23].
the physicochemical characteristics and microbial and heavy
metal contamination of the environmental matrices [19]. 2.3. Physicochemical Analyses of the Samples. Temperature,
However, no report is available yet on the petroleum hydro- pH, electrical conductivity (EC), and total dissolved solids
carbon profiles in both the water and sediment compartments (TDS) of the aqueous samples were determined on-site using
of the estuary, which is the subject of this current study. In this Hanna multiparameter probe (HI 98195), while turbidity,
paper, we report on the petroleum hydrocarbon fingerprints dissolved oxygen, and total suspended solids (TSS) were mea-
of water and bottom sediments of the Buffalo River Estuary sured using Hach instruments (Hach Company, USA) [24].
in the Eastern Cape Province, South Africa. Sediment samples were analyzed for moisture, organic car-
bon, and organic matter contents using gravimetric method
2. Materials and Method [25, 26].

2.1. Description of Study Area. The Buffalo River Estuary 2.4. Extraction of Petroleum Hydrocarbon from Surface Water
(33∘ 02󸀠 S; 27∘ 55󸀠 E) is the largest and one of the most important and Sediment Samples. Exactly 500 mL of water sample was
river estuaries in the Eastern Cape Province of South Africa spiked with 1 mL of 10 𝜇g/mL 1-chlorooctadecane (COD)
and located in the Buffalo City Metropolitan Municipality, used as surrogate standard, extracted thrice in a separating
East London [19]. It receives stormwater from the shipping funnel with 20 mL of n-hexane each time. The extracts
activities at the East London harbour, industrial effluents, were pooled together, dried with anhydrous sodium sul-
domestic wastes, urban runoff, and vehicular emissions from phate (20 g), and concentrated to about 2 mL using rotary
Steve Biko and Buffalo Bridges either directly or indirectly evaporator, ready for column cleanup [25, 27, 28]. Sediment
through its influent rivers. samples were air-dried for 5 days. Also, 10 g aliquot of the air-
dried sediment sample was blended with sufficient quantity
2.2. Cleaning of Glass Bottles and Sample Collection. Amber of anhydrous sodium sulphate (Na2 SO4 ) to remove moisture,
glass bottles used for sample collection were washed with tap spiked with 1 mL of 10 𝜇g/mL COD and extracted in a Soxhlet
water and detergent and rinsed with distilled water followed extractor with 200 mL of dichloromethane for 24 h. The
by acetone. Calibration standards, high performance liq- extract was allowed to pass through a glass funnel containing
uid chromatographic (HPLC) grade solvents, and analytical anhydrous sodium sulphate and reduced to approximately
grade reagents used for this work were sourced from Merck 2 mL using rotary evaporator. It was then solvent exchanged
(Germany) and Restek and Accustandard (USA). to n-hexane before the cleanup stage [25, 29].
Journal of Analytical Methods in Chemistry 3

Table 1: Description of the Buffalo River Estuary.

Study area Locations Latitude Longitude Depth (m) Description

A shallow entry point of the Buffalo River
E1 33.0306∘ S 27.8580∘ E 2.40 water into the estuary with pollution load
from major towns like King Williams
Town, Mdantsane, and Zwelisha.
An extension of the shallow part of the
E2 33.0279∘ S 27.8630∘ E 3.47 estuary, surrounded by hills with green
vegetations.
Second creek: the largest perennial
stream that accumulates stormwater,
E3 33.0261∘ S 27.8830∘ E 4.44 runoff, and leachates from Wilsonia
industrial area, residential zones, central
Buffalo River Estuary sewage treatment works, and a closed
solid waste landfill site.
First creek: this is another stream under
Steve Biko Bridge that contributes
nonpoint source pollution in the form of
E4 33.0243∘ S 27.8907∘ E 6.16 sewerage, stormwater, vehicular
emissions, and domestic and industrial
runoff into the estuary. The point is very
close to the Sea Spirit Fish Market that
uses some fishing boats for its activities.
This is the deepest sampling point,
E5 33.0233∘ S 27.8935∘ E 7.23 located very close to Yacht club under
Buffalo Bridge.

2.5. Silica Gel Cleanup and Separation. The water and sed- of concentrations of the n-alkanes that eluted from nC9 to
iment extracts were transferred into a 10 mm ID × 30 cm nC36 and UCM. Data analysis was done with the Agilent
chromatographic column packed with 10 g activated silica software [14, 32] while ANOVA and Pearson correlation were
gel slurry with about 2 cm anhydrous sulphate layer on performed using IBM SPSS Statistics 20, with the level of
top. The column was eluted with 20 mL of n-pentane to significance set at 0.01 [11].
obtain the aliphatic hydrocarbon fraction [30]. The eluates Limits of detection (LOD) for n-alkanes were determined
were concentrated to about 2 mL with rotary evaporator and from 8 replicate injections of a middle level calibration stan-
solvent exchanged to n-hexane. A control (blank) sample was dard [33, 34]. LOD was statistically calculated by multiplying
treated the same way as the real sample for quality assurance the standard deviation of the instrument response by “𝑡” value
[25, 31]. at 99% confidence level [35].

2.6. Gas Chromatography Analysis. All the cleaned sample 3. Results and Discussion
extracts were analyzed using Agilent 7820A gas chromato-
graph (GC) equipped with flame ionization detector and 3.1. Physicochemical Properties of Buffalo River Estuary Water
HP-5 fused silica capillary column (30 m × 0.32 mm ID × Medium. Table 2 shows the seasonal variation and the range
0.25 𝜇m film thickness). The carrier gas was helium at flow of values obtained for the physicochemical analyses of water
rate of 1.75 mL/min and average velocity of 29.47 cm/sec. from the five sampling locations in this study while Table 3
Exactly 1 𝜇L of the sample extract was injected in splitless demonstrates the Pearson correlation among the water qual-
mode at 300∘ C. The column temperature was held at 40∘ C for ity parameters.
1 min and then increased at 7∘ C/min to 320∘ C. The detector pH is an important indicator of water quality and pol-
temperature was 300∘ C [1, 28]. lution level in the aquatic environment. It is closely linked
The gas chromatograph was calibrated with n-alkane with biological productivity [36]. The pH of the water samples
working standards prepared in the range of 0.05–20 𝜇g/mL collected in the study area ranged between 7.4 and 9.3.
using n-hexane as diluent. Calibration curves were plotted The values recorded in summer were generally higher than
and average response factor was generated with Agilent autumn. However, there was no significant difference in the
Chemstation chromatography software for each analyte. The pH values across the 5 sampling stations. The South African
curves were linear with correlation coefficients ranging from permissible limit for coastal and marine water is 5.0–8.0
0.9846 to 0.9919. The unresolved peaks were quantified using [37] and the EU target limit is 6.0–9.0 [38]. The pH values
the response factor of nC15 in accordance with the method of recorded in this study were within the stipulated limits, except
Luan and Szelewski [32]. TPH was integrated with baseline- in January in four of the five stations (9.1–9.3). A significant
holding and peak sum slicing and then quantified as the sum positive correlation was observed between pH and other
4 Journal of Analytical Methods in Chemistry

Table 2: Monthly variation in the physicochemical parameters of the estuary water.

Summer Autumn
Parameters Range Total mean
January February March April May
pH 9.152 8.77 7.538 7.57 7.93 7.4–9.3 8.2 ± 0.7
Temperature (∘ C) 21.89 24.06 20.36 20.49 17.42 17–25 21 ± 2
Conductivity (𝜇S/m) 29.29 26.22 32.91 32.62 37.87 24.20–40.17 31.78 ± 4.80
Turbidity (NTU) 51.02 39.37 49.06 51.15 48.72 22.90–100.00 47.86 ± 19.58
Salinity (PSU) 26.29 24.21 27.04 26.34 27.74 22.84–29.10 26.32 ± 1.69
Dissolved oxygen (mg/L) 7.19 3.624 5.95 6.42 7.15 2.41–9.19 6.07 ± 1.62
Total suspended solids (mg/L) 9.93 10.77 11.23 11.50 92.13 1.33–446.67 27.11 ± 17.51
Total dissolved solids (mg/L) 18.89 16.11 20.9 21.06 19.04 13.50–22.75 19.20 ± 2.48

Table 3: Matrix of Pearson correlation among water quality parameters.

pH Temp Cond Turb Sal DO TSS TDS TPH

pH 1
Temp 0.888∗∗ 1
Cond 0.560∗∗ 0.381 1
Turb 0.325 0.317 0.201 1
Sal 0.861∗∗ 0.864∗∗ 0.670∗∗ 0.245 1
DO −0.032 −0.316 0.405∗ −0.183 0.047 1
TSS 0.037 −0.110 0.162 0.559∗∗ −0.076 0.020 1
TDS 0.451∗ 0.391∗ 0.835∗∗ 0.129 0.717∗∗ 0.406∗ −0.003 1
TPH 0.046 −0.072 0.354 0.094 0.043 −0.004 0.333 −0.011 1
Temp: temperature; Cond: conductivity; Turb: turbidity; Sal: salinity; DO: dissolved oxygen; TSS: total suspended solids; TDS: total dissolved solids; TPH: total
petroleum hydrocarbon. ∗∗ Correlation is significant at the 0.01 level (2-tailed). ∗ Correlation is significant at the 0.05 level (2-tailed).

parameters including temperature (𝑟 = 0.888; 𝑝 < 0.01), dissolved solids are sometimes used in its stead [40]. Effluent
conductivity (𝑟 = 0.560; 𝑝 < 0.01), and salinity (𝑟 = 0.861; or sewage discharge, as well as dissolved ions from soil and
𝑝 < 0.01) (Table 3). Reportedly, higher pH values have been rocks, are known to influence the values of conductivity and
linked to high concentration of carbonate in the water body salinity in the water column [41, 42]. Significant correlation
[16, 35]. (𝑟 = 0.670; 𝑝 < 0.01) observed between conductivity
Water temperature is another priority quality indicator and salinity as shown in Table 3 confirmed their positive
that plays a vital role in aquatic systems due to its ability relationship. pH also correlates positively with conductivity
to cause mortality and as well influence the solubility of (𝑟 = 0.560; 𝑝 < 0.01) as previously reported [39].
dissolved oxygen needed by the aquatic lives [36]. In the Total dissolved solids (TDS) value is a measure of inor-
current investigations, temperature varied from 17 to 25∘ C ganic and organic materials present in water, of which salt
in the water column. Temperature was generally higher in forms the principal constituent [42]. The TDS of the estuary
summer than in autumn, though with no statistical difference water ranged between 13.50 mg/L and 22.75 mg/L. The trend
among the sampling stations, although all the values obtained was similar to that of the conductivity where the values were
throughout the study period fell within the South African higher in autumn than in summer. Although South Africa
threshold limit of 15–35∘ C [33]. Temperature also correlates and EU do not have any target value for TDS in the coastal
positively with salinity (𝑟 = 0.864; 𝑝 < 0.01) and TDS and marine water, the results obtained were higher than
(𝑟 = 0.391; 𝑝 < 0.05) as earlier reported but no correlation 10 mg/L set as target value for estuary and coastal water in
with dissolved oxygen was observed [39]. the Darwin Harbour region [43]. TDS in this work correlate
Conductivity is defined as a measure of the ability of a positively with salinity (𝑟 = 0.717; 𝑝 < 0.01) in agreement
solution to conduct electrical current through the water [24]. with the report of Chigor et al. [11], conductivity (𝑟 = 0.835;
It is usually higher in saline compared to freshwater systems 𝑝 < 0.01), pH (𝑟 = 0.451; 𝑝 < 0.05), temperature (𝑟 = 0.391;
[36]. The conductivity of the estuary water varied from 24.20 𝑝 < 0.05), and dissolved oxygen (𝑟 = 0.406; 𝑝 < 0.05)
to 40.17 𝜇S/m (Table 2). It was generally lower in summer as shown in Table 3. A general increase in concentration
(mean = 27.76 𝜇S/m) than in autumn (mean = 34.47 𝜇S/m) was observed as the water depth increases [40]. Waters with
and showed a positive relationship with depth, increasing high TDS cause cells to shrink, disrupt organisms’ movement,
as the depth increases. A similar trend was observed in the and make them afloat or sink beyond their normal range.
salinity. There is no standard guideline set for the control High TDS value indicates high alkalinity or hardness and can
of conductivity in marine water, although limits set for total consequently affect taste of the water column [40].
Journal of Analytical Methods in Chemistry 5

Table 4: Average concentration of hydrocarbons and sources diagnostic ratios in the estuary water (𝜇g/L).

Summer Autumn
Parameters Range Total mean
January February March April May
Total n-alkanes 77.63 161.37 68.29 53.47 177.34 15.46–328.59 105.38 ± 17.01
UCM 31.23 45.15 45.36 0 150.31 1.67–278.71 66.66 ± 16.78
TPH 102.61 174.24 104.58 53.47 297.59 7.65–477.07 146.50 ± 27.96
C15–C19 (odd) 0 0 16.61 0 16.97 0–44.33 6.72 ± 2.42
C18–C22 (even) 0 0.82 5.21 4.73 13.61 0–33.45 4.88 ± 1.69
C25–C35 71.21 108.38 2.77 6.54 88.17 0–228.93 55.41 ± 13.81
L/H 0 0.01 4.66 0.29 0.29 0–7.56 1.00 ± 0.40
C31/C19 0 0 0 0 5.53 0–16.98 2.46 ± 1.11
U/R 0.30 0.32 0.45 0 0.68 0–1.41 0.35 ± 0.09

Dissolved oxygen (DO) is another important component 1.33 mg/L to 447 mg/L showing the same trend of decrease as
of aquatic system [16, 36, 41]. It is a measure of the level of free, the water depth increases. There was no significant difference
noncompound (nonbonded) oxygen dissolved in the water in TSS among the five (5) sampling points. Higher turbidity in
column [44]. DO enrichment in surface water is permitted the nearshore waters may be due to particulates arising from
through atmospheric exchange. However, thermal or salinity clay and silts from shoreline erosion, resuspended bottom
stratification and anthropogenic activities involving organic sediment, organic detritus from water discharges, urban
matters may result in DO depletion, suppressing respiration runoff, industrial effluents, and excess phytoplankton growth
and causing huge die-offs of recreationally indispensable fish [24, 47].
[39, 45]. The results of the DO measured in the estuary
water ranged as 2.41–9.19 mg/L (Table 2). The least average 3.2. Levels of n-Alkanes and Total Petroleum
DO was observed in summer when the water temperature Hydrocarbons in Water and Sediment Samples
was the highest, supporting an inverse relationship between
the two parameters as evidently revealed (Table 3) [36]. 3.2.1. Quality Control. The quality control study was carried
Although there was no significant difference spotted between out by spiking surrogate standard into each water and
the stations, however a gradual increase was observed from sediment sample before extraction and the recoveries which
summer to autumn and also as depth increases. The min- were within the acceptable range of 40–140% were used for
imum requirement of dissolved oxygen in coastal water is correcting the final concentrations of the analyte compounds
4 mg/L [39]. DO concentrations recorded in this study area extracted. Limit of detection obtained for the n-alkanes
were higher than the standard limit in all the sites except varied from 0.06 to 0.13 𝜇g/L and the relative standard
only once in summer when a lower value of 2.41 mg/L was deviations (RSD) were in the range of 3.61 to 8.32% [48, 49].
obtained at site E2 [46].
Turbidity and total suspended solids (TSS) are other 3.2.2. Levels of Petroleum Hydrocarbons in the Water Samples.
quality parameters with significant relationship. Turbidity Total petroleum hydrocarbons (TPH) in the surface water
is a measure of water clarity or muddiness resulting from of Buffalo River Estuary were evaluated in all the sam-
the collection of dissolved and suspended solids, making pling points. The results covering two seasons (summer and
light scattered and absorbed instead of being transmitted in autumn) are summarized in Table 4 and spatial distribution
straight lines [47]. Elevated turbidity in waters is often linked of petroleum hydrocarbons in the water matrix is depicted in
with the likelihood of microbiological pollution [41]. The Figure 2 below.
current investigation had mean turbidity of 47.86 ± 19.58 The TPH concentration in the study varied widely across
NTU for the estuary water in the range of 22.9–100 mg/L. the 5 locations from 7.65 to 477.07 𝜇g/L. The highest con-
Turbidity was generally higher in autumn than in summer. centration was observed at site E3, followed by sites E4 and
The highest value of 100 mg/L was obtained at E3 (second E1 as shown in Figure 2. Among these, sites E3 and E4
creek) in May when fresh industrial effluents were discharged which were the second and first creeks receive sewerage,
into the estuary and the lowest was also recorded the same stormwater, and runoff from industrial (including Gately,
month at E5 (22.9 mg/L). There was a gradual decrease in West Bank Hood, Woodbrook, and East London Harbour)
turbidity values as the depth increases and from summer to as well as the residential and commercial areas in the East
autumn. Turbidity recorded at the shallowest site (E1) was London metropolis. Site E1 was located at the entry point of
significantly different from the values obtained from the two the estuary where Buffalo River freshwater is discharged with
deepest sites, E4 (𝑝 < 0.01) and E5 (𝑝 < 0.05). pollution loads from some major towns like King Williams
Similarly, significantly high TSS was recorded in May at Town, Zwelisha, and Mdantsane. Lowest concentrations of
E3 (447 mg/L). This could be attributed to the fresh discharge TPH however occurred in sites E5 and E2 with seemingly
of effluents sighted at the site during the time of sampling. less anthropogenic activities [19, 20]. Depth may also have
Total suspended solids in the estuary generally ranged from contributed to the low concentration of TPH in site E5 [50].
6 Journal of Analytical Methods in Chemistry

180 450000
160 400000

Mean concentrations (
휇g/kg)

Mean concentrations (
휇g/L)

140 350000
120 300000
100 250000
80 200000
60 150000
40 100000
20 50000
0 0
E1 E2 E3 E4 E5 E1 E2 E3 E4
Sampling points Sampling points
Series 1 Series 1
Figure 2: Spatial variation of TPH in the Buffalo River water Figure 3: Spatial variation of TPH in the Buffalo River sediment
samples. samples.

No particular trend was observed in the distribution rocky substratum of site E5 made sediment sampling difficult
of TPH across the whole period of study. Generally, the throughout the span of this study. There was no doubt that
concentrations were lower in summer than in autumn as larger contribution of pollutants in the estuary sediment was
reported by Maktoof et al. [51]. This could be linked with the from Buffalo River water discharge at E1, as well as the intro-
collection of samples mostly during the high tide in autumn duction of the industrial effluents and leachates from the old
compared to summer [52] and also because larger amount of land fill site at E3 among others [19, 20]. Notwithstanding, the
pollutants are swept into water bodies in autumn as the level statistical tests conducted revealed no significant difference in
of rainfall increases [53]. The highest concentration which the levels of TPH determined between the sampling stations.
was recorded at site E3 in May was probably due to the The temporal distribution of TPH in the sediment follows this
fresh discharge of effluent at the time of sampling. Statistical order: April > January > May > March > February (Table 5).
analyses however did not show any significant difference in Petroleum hydrocarbons in the sediments were found much
the TPH concentrations obtained across the stations. The higher in autumn with mean concentration of 233.62 mg/kg
total mean concentration of TPH (146.50 ± 27.96 𝜇g/L) in all than in summer (160.22 mg/kg) due to the upward push and
the sites was lower than the EU acceptable standard limit for resuspension of contaminants occasioned in some cases by
hydrocarbons (300 𝜇g/L) in estuary and harbour basin water the high tidal forces in the aquatic environment [52, 61].
[38]. Although no sediment guideline is in place for total
The level of water TPH from this study was significantly petroleum hydrocarbons, nevertheless, four levels of
lower compared to values reported in some regions includ- petroleum hydrocarbon pollution were suggested for the
ing Bohai Bay of China [54], Strait of Johor, Peninsular assessment of marine sediments [50]. They were unpolluted
Malaysia [55], seawater of North Cape [56], groundwater (10–15 mg/kg), slightly polluted (15–50 mg/kg), moderately
samples collected from some communities in Rivers State, polluted (50–200 mg/kg), and heavily polluted statuses
Nigeria [57], surface water from Ubeji in Warri, Nigeria (>200 mg/kg). This was not entirely different from the
[58], and the surface water from the neighbourhood of Nige- respective target and intervention values of 50 mg/kg and
rian National Petroleum Corporations Oil Depot in Apata, 5,000 mg/kg set as environmental guidelines for soil and
Ibadan Metropolis, Nigeria [59]. However, some studies were sediment TPH by the Department of Petroleum Resources,
reported with lower values of TPH than obtained in this study Nigeria [62, 63]. In light of the above, the TPH concentrations
in other parts of the world. Examples include water samples of the Buffalo River Estuary sediments were largely below
from Main Outfall Drain in Al-Nassiriya City/Southern Iraq the intervention value, ranging from “moderately polluted”
[51], water samples from Setiu Wetland [60], Terengganu in summer to “heavily polluted” in autumn [50, 64].
coastal waters from Malaysian west coast [55], and Dungun Petroleum hydrocarbon levels in the sediment compart-
River basin water, Malaysia [23]. ment of this study area were found comparatively lower
than those reported for the sediments from Ceuta harbour,
3.2.3. Levels of Petroleum Hydrocarbons in the Sediment Sam- North Africa [65], and Arabian Gulf, Kuwait [50]. However,
ples. In this study, the concentrations of TPH in the estuary the concentrations were a little higher than those from the
sediments expressed on dry weight basis are presented in Arabian Gulf [66], Bohai Bay, China [67], Khowr-e Musa Bay
Table 5. The values ranged from 12.59 to 1,100 mg/kg. As [22], and Musa Bay [68]. Nonpolluted sediments reported
shown in Figure 3, site E1 recorded the highest concentration in some studies include those from coastal area of Putatan
of TPH, followed by site E3 (second creek) while the lowest and Papar, Sabah [69], Main Outfall Drain in Al-Nassiriya
was obtained from site E4, which could possibly be related City, Southern Iraq [51], and coastline and mangroves of the
to the higher depth of water at the station [50]. However, the northern Persian Gulf [70].
Journal of Analytical Methods in Chemistry 7

Table 5: Average concentration of hydrocarbons and sources diagnostic ratios in the estuary sediment (mg/kg).

Summer Autumn
Parameters Range Total mean
January February March April May
Total n-alkanes 55.35 38.45 25.48 89.02 35.95 2.04–169.89 49.53 ± 9.98
UCM 168.43 58.20 75.68 395.65 84.48 2.70–930.33 160.28 ± 54.19
TPH 223.78 96.65 101.16 484.68 120.43 12.59–1,100 209.81 ± 63.82
C15–C19 (odd) 1.08 0.44 0.92 2.88 0.71 0.25–6.30 1.23 ± 0.31
C18–C22 (even) 2.15 1.98 1.67 5.35 1.74 0.95–11.16 2.62 ± 0.54
C25–C35 43.53 29.26 18.33 63.60 19.33 6.43–127.12 35.62 ± 7.90
L/H 0.15 0.08 0.08 0.07 0.17 0.04–0.32 0.11 ± 0.02
C31/C19 14.50 26.38 3.51 3.80 5.08 2.30–35.29 10.95 ± 2.33
U/R 1.53 1.54 3.19 3.82 2.19 0.27–5.77 2.47 ± 0.38
CPI 3.00 2.99 1.94 1.68 1.52 1.14–4.11 2.26 ± 0.20
ACL 29.37 29.37 28.42 28.92 28.53 27.38–30.69 28.94 ± 0.16
UCM: unresolved complex mixture; TPH: total petroleum hydrocarbon; L/H: low molecular n-alkanes/high molecular n-alkanes; U/R: unresolved n-
alkanes/resolved n-alkanes; CPI: carbon preference index; ACL: average carbon chain length.

Table 6: Percentage moisture, organic carbon, and organic matter contents of the sediments.

Moisture (%) Organic carbon (%) Organic matter (%)

Range 45.01–67.86 3.12–8.94 5.39–15.42
Mean 59.03 ± 6.85 6.14 ± 1.35 10.59 ± 2.32

3.3. TPH Relationship with Percentage Moisture, Organic Car- Table 7: Pearson correlations among the sediments quality param-
bon, and Organic Matter Contents of the Sediments. Table 6 eters.
shows the percentage moisture, organic carbon (OC), and % moisture % OC % OM TPH
organic matter (OM) of the estuary sediments. The muddy
% moisture 1
sediment samples contain a large percentage of water in the
% OC 0.316 1
range of 45.01–67.86%, with an overall average of 59.03%.
The sediment grains were relatively small, having an average % OM 0.316 1.000∗∗ 1
composition of 58.35% fine sand, 30.43% very fine sand, and TPH 0.133 0.665∗∗ 0.665∗∗ 1
∗∗
11.22% coarse silt determined by sieving. Both OC and OM Correlation is significant at the 0.01 level (2-tailed).
in muddy sediments were considered to play a significant role
in the accumulation and release of various micropollutants in
the aquatic environments [50]. been of great advantage in the identification of pollution
sources in the estuarine and marine environments [9]. Many
Organic carbon in the sediment samples ranged from
mathematical ratios and indexes like major hydrocarbon
3.12 to 8.94% (mean = 6.14%), whereas organic matter varied
(MH), ratios of low molecular weight to high molecu-
between 5.39% and 15.42% (mean = 10.59%). Statistical
lar weight n-alkanes (L/H), unresolved complex mixture
analysis showed a significant difference (𝑝 < 0.1) in
(UCM), average carbon chain (ACL), carbon preference
the moisture contents of the sediments collected from E2
index (CPI), weathering index, and C31/C19 have been used
and E4. However, no significant difference was observed
to identify the origins of n-alkane in the environment [74, 75].
among the stations in relation to OC and OM. The total
petroleum hydrocarbon positively correlate with OC (𝑟 =
0.665; 𝑝 < 0.01) and OM (𝑟 = 0.665; 𝑝 < 0.01) 3.4.1. Distribution of n-Alkanes. Various ways through which
(Table 7), indicating a direct relationship among the three hydrocarbons come to the surface of marine and coastal
parameters. This relationship was further checked in a plot waters include anthropogenic activities, biosynthesis (pro-
of OC against TPH. The plot yielded a straight line with duction of hydrocarbons by some living organisms in the
𝑟2 = 0.1043 (Figure 4). High concentration of petroleum aquatic environments), and geochemical processes (e.g.,
hydrocarbons in the sediments of the river estuary testifies to seepage). Some anthropogenic activities involving indus-
the role of sediment as a sink for organic micropollutants [71]. tries, oil operations, and urban undertakings could generate
Petroleum hydrocarbons concentration is usually higher in substantial quantity of hydrocarbons in the marine waters.
muddy sediments compared to the coarse ones, establishing However, hydrocarbons from biosynthetic marine origins are
a strong relationship between grain size and TPH [50, 72, 73]. always present in trace quantity [9, 74].
Concentrations of total 𝑛-alkanes in the estuary vary
between 15.46 and 328.59 𝜇g/L in the water samples and from
3.4. Hydrocarbon Source Identification Using Molecular Mark- 9,889 to 169,885 𝜇g/kg in the sediment samples as shown in
ers. The use of n-alkanes as a molecular marker has Tables 4 and 5. Clear indication of different sources is offered
8 Journal of Analytical Methods in Chemistry

80000 The results obtained from the water samples showed the
70000 L/H ratios greater than one (1) in the first two stations (E1
and E2), indicating fresh release of petroleum hydrocarbons
60000 from agricultural, residential, and/or industrial activities
50000 that entered the estuary through rivers and streams in the
TOC (
휇g/kg)

y = 0.0184x + 57095
R2 = 0.1043 watershed. However, the remaining three sampling locations
40000
yielded ratios lower than one (unity). Sediments samples
30000 from all the stations also gave L/H ratios lower than 1,
20000
suggesting hydrocarbons from natural sources [79].

10000
3.4.3. Long Chain Hydrocarbons/Short Chain Hydrocarbons
0 (LHC/SHC). Short chain hydrocarbons (SHC) are the n-
0.00 100,000.00 200,000.00 300,000.00 400,000.00 alkanes which are below and up to nC26 (e.g., nC15, nC17,
TPH (
휇g/kg) and nC19). They are derived from planktonic and benthic
TOC algal sources, whereas long chain hydrocarbons (LHC) are
Linear (TOC) the n-alkanes up to nC26 (e.g., nC27, nC29, and nC31) which
are mostly from vascular plants sources. They are known to
Figure 4: Plot of TOC versus TPH in the water matrix of Buffalo be more resistant to decomposition than their short chain
River Estuary.
counterparts. The ratio is used to evaluate the dominance
of vascular plant and phytoplanktons in the marine envi-
ronments. While the ratio of LHC/SHC between 0.21 and
by the strong presence of some specific normal alkanes.
0.80 indicates phytoplankton sources, value in the range of
Examples include nC25–nC35 which indicate biogenic input
2.38 to 4.33 suggests a mixture of both sources. Higher value
(terrestrial and vascular plants), and a strong dominance of
greater than 4.0 shows the dominance of terrestrial plant
odd over even numbered n-alkanes could also suggest the
waxes [78, 81].
same origin. The presence of nC15, nC17, and nC19 n-alkanes
indicates inputs from phytoplankton and algae marine bio- LHC = sum of nC27, nC29, and nC31.
genic sources. Dominance of even carbon n-alkanes such SHC = sum of nC15, nC17, and nC19.
as C16, C18, and C20 indicate petroleum hydrocarbons
pollution from anthropogenic sources. Likewise, the presence Average LHC/SHC ratio obtained in this study ranged
of nC12 and nC14 alkanes indicates microbial biogenic origin between 11.18 and 17.71 in the 4 sediment stations, an indi-
[27, 76, 77]. cation of a significant input from terrestrial plant waxes.
Distribution of n-alkanes in the study revealed that the
most prominent ones in the water samples were nC9–nC12, 3.4.4. Unresolved Complex Mixture (UCM) and Weathering
nC15, nC17, nC19, and nC26–nC36 whereas, in the sediment Index (WI). The UCM is considered a mixture of branched
samples, nC10–nC12, nC18, nC20, nC22, and C22–nC36 and cyclic hydrocarbon structures, including many of their
dominate. Generally, heavier hydrocarbons were more in structurally complex isomers which are unresolvable by
abundance than the lighter ones and odd carbon n-alkanes the capillary columns of gas chromatograph [74, 80]. The
seemed to be a little more dominant than the even carbon n- aliphatic hydrocarbons are less soluble than the aromatic
alkanes as was also reported by Ahmed et al. [28]. Aliphatic compounds which are relatively more mobile in water. The
hydrocarbons in the water compartment of the estuary branched aliphatics are even less water-soluble than the
are principally from biogenic sources. However, the origins straight-chained alkanes. Hence, they concentrate more in
of the n-alkanes in the sediments are both biogenic and the sediment compared to the water column [5]. Although
anthropogenic (possibly from fishing, industrial storm water, UCM are mostly present in the higher molecular range
and urban runoff) [78]. of the hydrocarbons, few exist in the lower range as well.
The lower range UCM can easily be evaporated unlike
3.4.2. Low Molecular Weight/High Molecular Weight n- their counterparts in the higher range category and their
Alkanes (L/H). Ratio of low molecular weight n-alkanes presence in the marine environments generally indicate
(C15–C20) to high molecular weight 𝑛-alkanes (C21–C34) is bacterial degradation of old petroleum products or chronic
another marker being used for the determination of 𝑛-alkanes oil pollution; however fingerprinting information available
sources [28, 78]. Low molecular weight hydrocarbon usually from their data is very limited [9, 14, 82].
dominates in a fresh oil release, giving a ratio greater than Figures 5 and 6 revealed the presence of UCM in some
one. L/H is an indicator of the freshness of the hydrocarbons of the samples analyzed (mostly sediments) appearing as a
released into the environments. However, fast degradation unimodal or sometimes as a bimodal hump in the range of
of these lower molecules in crude oil can decrease the ratio nC12 to nC15 and nC22 to nC35. The UCM concentrations
significantly to a value below unity. The L/H ratio below in the sediments varied between 2,700 and 930,328 𝜇g/kg
1 (unity) reveals natural input from marine and terrestrial (mean = 160,278 ± 54.19 𝜇g/kg) and in the water samples
biogenic sources, and ratios around and above 1 indicate between 67 and 279 𝜇g/L (mean = 66.66 ± 16.78 𝜇g/L).
hydrocarbons from petroleum sources [79, 80]. Meanwhile, the abundance of the higher molecular weight
Journal of Analytical Methods in Chemistry 9

FID1 A, front signal (115F1501.D) Table 5 shows CPI values obtained from this study in
225 the range of 1 and 3, increasing towards the ocean. This
200
175 shows that anthropogenic input decreases as marine input
150
(pA)

125 increases. Generally, the results indicate that Buffalo River

100
75 Estuary is dominated by n-alkanes from both natural and
50 anthropogenic origins [9, 84].
25
5 10 15 20 25 30 35
(min) 3.4.6. C31/C19. This is another important ratio used to
differentiate the sources of n-alkanes in water. The presence
Figure 5: Chromatogram of a typical sediment sample from E1. of nC31 is an indication of terrestrial biogenic hydrocarbons,
whereas nC19 suggests marine biogenic inputs. The C31/C19
FID1 A, front signal (102F0201.D) ratio is therefore used to assess the dominance of n-alkanes
from either of the two sources. While ratio below 0.4 reveals
100 marines sources, any value above 0.4 is an indication of
80 land derived or nonmarine hydrocarbons [28, 78]. Although
(pA)

60 water samples from site E1 had no nC31, other sampling

40 locations gave higher values than 0.4 (Tables 3 and 4), which
20 are indicative of hydrocarbons mainly from anthropogenic
5 10 15 20 25 30 35 origins.
(min)

Figure 6: Chromatogram of a typical sediment sample from E4. 3.4.7. Average Carbon Length (ACL). Average carbon length
is an index used in the evaluation of odd carbon dominance
per molecule in environmental samples to establish the link
with higher plants normal alkanes. The value is usually
hydrocarbons (>nC23) over the lighter ones suggests no constant in nonpolluted sites but fluctuates with depleted
recent contamination in the aquatic environment [14, 83]. values in the areas polluted with petroleum hydrocarbons
Another useful tool employed for the assessment of [85]. The values were calculated using the formula below as
the presence of some important crude oil residues is the previously demonstrated [86, 87].
ratio of the unresolved components to that of the resolved
ones (U/R), otherwise called weathering index. Higher ratio ACL value
greater than 4 is usually a criterion for important petroleum
residues [84]. In this study, U/R in the sediment samples 25 (nC25 ) + 27 (nC27 ) + 29 (nC29 ) + 31 (nC31 ) + 33 (nC33 ) (2)
= .
generally ranged from 0.27 to 5.77. Higher ratios greater than C25 + C27 + C29 + C31 + C33
4 were observed only in autumn (March and April) at stations
E1 and E3, suggesting pollution arising from the inflow of ACL in the Buffalo River Estuary sediments ranged between
urban and industrial runoffs, effluent discharge, leachate 27.38 and 30.69 (Table 5). This shows about 3.31 units of
from a nearby dumpsite, and stormwater from the nearby changes. The little deviations from the mean value were
harbour where shipping activities are ongoing among other noticed in January, February, and May. Three of the four
possible sources. However, the maximum value recorded stations were involved in the fluctuations, except E1 that had
in the water samples was 1.41, indicating a relatively low constant value close to the mean all through. The lowest ratio
petroleum contamination in the water column. Degraded was obtained in May at E2 (27.38) and the highest in February
petroleum residues may stay bound to soils/sediments for at E4 (30.69). The slight fluctuations observed across the
years and may bring about a short-term damage to aquatic sampling stations indicate a little anthropogenic contribution
lives and also impact the recreational use of the water body to the abundance of hydrocarbons and corroborate previous
negatively [5]. reports elsewhere [9, 86]. The results show a positive signif-
icant correlation with CPI (𝑟 = 0.699; 𝑝 < 0.01), though
with a lower regression (𝑅2 = 0.3535) (Figure 7), indicating a
3.4.5. Carbon Preference Index (CPI). This is an indicator for rise in ACL as CPI increases [29]. This relationship confirms
dominance of natural hydrocarbons over the anthropogenic that hydrocarbons in the Buffalo River Estuary are from both
ones. It reveals the ratio of odd to even carbon number n- natural and anthropogenic origins because the CPI values
alkanes from different categories. Terrestrial vascular plants were between 1 and 3 [78].
sourced hydrocarbons are identified with CPI values in the
range of 3 to 10 while lower value close to 1 indicates
petroleum and anthropogenic activities such as combustion 4. Conclusion
of fossil fuel, effluent discharge, and agricultural and wood
Physicochemical parameters of the Buffalo River Estuary
rubbles mostly from industrial and urban areas [9, 28, 84].
water were assessed in this study. Almost all were found
within the acceptable threshold limits except pH, turbidity,
(C25 –C33 ) (C –C )
CPI25–33 = 0.5 ∗ [ ] + [ 25 33 ] . (1) and total suspended solids that slightly exceeded, especially
(C24 –C32 ) (C26 –C34 ) in May when the water was disturbed with a fresh and
10 Journal of Analytical Methods in Chemistry

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