Physicochemical parameters
The data from this research represent findings at the time of collection and may not necessarily reflect the seasonality to which the bay is truly exposed. The main characteristics frequently employed to assess the physicochemical properties of water are summarized in Table 3, amongst which pH, DO, COD, BOD5, sulphate, phosphate, oil and grease, and most importantly, the potentially toxic metals were the main focus discussed.
The pH values of Apapa Bay's water were slightly alkaline, ranging from 7.03 ± 0.15 to 7.85 ± 0.21 (Table 3). These results aligned with the National Environmental Standards and Regulations Enforcement Agency, NESREA (2011) permissible limit of 6.5 – 8.5 for drinking and recreational purposes. Amongst notable characteristics of the marine environment is the stability of its pH, maintained by the biological activity of the coastal zone and is astonishingly constant over a specific area. Similar views of the pH results have been independently reported by Onyema et al. 2009; Balogun et al. 2011; Onyema 2013; on water samples within Lagos such as Badagry Creek, Lagos Habour and Iyagbe Lagoon.
Amongst the water quality control measures is the concentration of dissolved oxygen (DO). It is the amount of oxygen present in water, and its unit is mg/L. It is affected by the presence and destruction of organic substances and the self-purification capacity of the water body (Ma et al. 2020). As presented in Table 3, the dissolved oxygen concentrations from this study ranged from 2.59 ± 0.302 to 4.47 ± 1.316 mg/L. This is similar to those reported for many other polluted Nigerian waters, including the 3.90 to 4.95 mg/L of Apese lagoon (Victor and Onomivbori 1996), and the reported concentration range of 2.41 to 4.95 mg/L for some polluted water bodies in Nigeria (Edokpayi and Osimen 2001; Davies et al., 2009; Ogunfowokan et al. 2005). Some activities such as shipping, dredging, channeling, and anthropogenic and industrial activities release larger volumes of oxygen-demanding pollutants into the water system, thus contributing to low DO of the water. This leads to the extremely unpleasant nature of the water (Czarnota et al., 2023).
At 25oC, the permissible limit of dissolved oxygen concentrations in unpolluted water ranges between 8 and 10 mg/L and concentrations ranging from 2 - 5 mg/L adversely affect aquatic life (Binod and Bhoj 2012). However, a concentration below 2 mg/L usually causes the death of aquatic animals (Small et al. 2014). Due to low dissolved oxygen present in water at high temperatures, the sustainability of aquatic organisms is affected. This study's DO values were below the suggested threshold. Major characteristics of polluted water is the low levels of DO cause by elevated BOD5 and COD due to effluent waste materials discharged from ships and jetties into surface water. The value of BOD5 is always lower than that of COD because many organic substances cannot oxidize biologically but can be oxidized chemically. Effluent waste, especially oil materials discharge from ships and jetties causes higher values of BOD5 and COD. Generally, biological oxidation of organic pollutants is practically impossible. This accounts for higher COD values when compared with BOD5. In this study, the principle was observed as COD concentration ranged from 199.1 ± 10.2 to 236.7 ± 14.8 mg/L while BOD5 concentration ranged between 36.5 ± 4.6 and 72.4 ± 2.6 mg/L. The ratio of BOD5 and COD varies widely from one terminal to another, an indication of differences in the types of organic compounds that might be present. The levels of BOD5 and COD were not in agreement with the NESREA’s limit of 6.0 mg/L and 30.0 mg/L, respectively for wastewater. High level of COD is an indication of harmful conditions and the presence of non-biologically oxidizable matter, and high levels of BOD5 indicates that there may not be enough oxygen present in the water of Apapa Bay for aquatic organisms such as crabs, crayfish, toad, and fish.
The concentrations of sulphate in this study ranged from 36.92 ± 14.10 to 64.28 ± 11.10 mg/L. However, according to NESREA (2011), the maximum contaminant level in wastewater is 500 mg/L. Therefore, the concentration of sulphate in Apapa Bay water is lower than the permissible limit. Most tropical waters have low nutrient values, a common feature of natural and polluted waters (Christian et al. 2021). The level of sulphate recorded in this study is suggestive of organic pollution, which agrees with the work of Tolulope et al. (2019).
In Nigeria, NESREA’s maximum permissible limit for phosphate in polluted water is < 5 mg/L. Literature reports shows that studies of water bodies, for example, Lagos lagoon, showed low phosphate levels. Balogun et al. (2011) reported the phosphate levels of 0.57 – 1.60 mg/L for Lagos harbor, and Onyema et al. (2009) reported 0.28 – 2.50 mg/L for study of Badagry creek. The results of Chukwu and Akinyanmi (2018) were 2.05 – 4.34 mg/L for Apapa Waters, and Davies et al. (2009) reported 0.14 – 0.35 mg/L for Elechi Creek. However, the concentration of phosphate recorded in Apapa Bay water was at low range of 0.363 ± 0.116 mg/L to 0.652 ± 0.094 mg/L. Therefore, it is within the range of phosphate values reported in the above-mentioned studies. Phosphate is an essential part of nutrient needed by lants and animal for growth, hence its low concentration or absence would affect the growth of aquatic organism in Apapa Bay. Aside from the domestic and industrial effluents discharged into the bay, the level of phosphates (0.363 to 0.652 mg/L) recorded in this study could be attributed to the discharge of ballast water from ships and cargo sailing constantly on the water.
The presence of oil and grease in wastewater is a threat to wastewater treatment systems. In excess amounts, they may impede aerobic biological processes, leading to inefficiency and increased cost of wastewater treatment. When discharged in wastewater, they may cause surface films and shoreline deposits, causing environmental degradation (Wanda et al. 2021). In this study, the concentrations of oil and grease from Apapa Bay, presented in Table 3, are 13.03 ± 0.60 mg/L; 16.02 ± 1.17 mg/L; 16.33 ± 0.21 mg/L and 21.65 ± 0.28 mg/L for terminals A, B, C and D respectively. These values are above the regulatory authority, NESREA permissible limits of 0.1 mg/L.
Potentially toxic metals analysis
Examined from different sampling sites, the distribution of potentially toxic metals, namely Cd, Fe, Pb, and Cu, in the Apapa Bay bottom sediments has been analyzed to help understand the influence of shipping activities on the water quality of the Bay. The sampling sites are Terminals A, C and D, and Takwa Bay serves as control due to its non-shipping activities. The distribution patterns were represented by interpolating the metal concentration from the plotted calibration curve. Table 4 depicts the mean concentrations of potentially toxic metals analyzed. The results were then compared with some previously studied bays of the world, presented in Table 5. There is a wide range of values of the mean concentrations of the potentially toxic metals against those obtained from Takwa Bay (control) where the effect of shipping activities was low except copper which has the same values in almost all the Terminals; Cd (1.210 ± 0.001 to 3.024 ± 0.057 mg/kg); Fe (30.000 ± 0.884 to 35.625 ± 2.946 mg/kg); Pb (1.756 ± 0.170 to 65.902 ± 6.730 mg/kg); and Cu (10.859 ± 0.907 to 13.423 ± 0.907 mg/kg) while in Takwa bay (control), mean concentrations Cd (0.600 ± 0.001 mg/kg); Fe (6.876 ± 0.010 mg/kg); Pb (8.585 ± 0.510 mg/kg); Cu (10.859 ± 0.910 mg/kg).
Cadmium ranged from 1.210 ± 0.001 mg/kg (Terminal C) to 3.024 ± 0.057 mg/kg (Terminal A), and the control (Takwa bay) showed a low value of cadmium (0.600 ± 0.001 mg/kg). The cadmium level was lowest at Terminal C. These values are high compared with many other studies, such as 0.136 mg/kg (Wei et al. 2023); 0.4 mg/kg (Hakima et al. 2017); 0.11 mg/kg (Qiao et al. 2015), 0.12 mg/kg (Xu et al. 2015) and 0.35 mg/kg (Ebru 2012). Aside from the nearness of many industries to the study area that might increase the level of cadmium through their discharge of untreated wastewater, major remote sources with respect to shipping activities could be from ship construction, repair activities in the dockyard, and the use of motor vehicle tire rubber used by ships to maintain buoyancy. Cadmium is one of the major byproducts of zinc refining, a non-corrosive pigment used in the manufacturing of ship paint (Gunnar et al. 2015). It is extremely toxic (Janja et al. 2022), and studies have reported that consumption of aquatic organisms with high levels of cadmium leads to cardiovascular and skeletal malformation (Balali-Mood et al. 2021).
The Apapa Bay sediment concentrations for Pb ranged from 65.902 ± 6.730 mg/kg (Terminal C and D) to 1.756 ± 0.170 mg/kg (Terminal A), and the control (Takwa Bay) showed a low value of Pb (8.585 ± 0.510 mg/kg). The concentrations of Pb in the sediment samples of Terminal A and D are higher than the reported values of Weihai Bay, China (Wei et al. 2023); Upper Gulf, Thailand (Qiao et al. 2015); and Laizhou Bay, China (Xu et al. 2015). Meanwhile, Terminal B and Takwa Bay results are lower than the above-mentioned Bays. Petroleum products, certain geological formations, and anthropogenic sources in the nearby communities are the study area's main sources of lead (Pb). The most common form of Pb in the aquatic environment is Pb2+, and the dimethyl lead (CH3)2Pb2+ is a very good example (Chowdhury et al. 2022). Dimethyl lead (CH3)2Pb2+ is used to increase the octane rating of oil, making oil its major source of exposure. Therefore, the primary method of consuming this metal is through food, and consumption of aquatic organisms from the research region may raise the fatal dose in the human body. The toxicity of Pb has been adequately reported in some environmental studies, such as Hauptman et al. (2017), Wani et al. (2015), and Mandal et al. (2023).
The Apapa Bay sediment concentrations for Cu ranged from 10.859 ± 0.907 mg/kg (Terminal C, D, and Takwa Bay) to 13.423 ± 0.907 mg/kg (Terminal A). In this study, both Terminals C and D have the same mean concentration, while it is higher in Terminal A, probably as a result of the heavy use of copper mounts in shipbuilding. The level of Cu in all Terminals and that of Takwa Bay is lower than the reported values in literature such as Wei et al. (2023); Hakima et al. (2017); Qiao et al. (2015); Jamshidi and Saedi (2014); Xu et al. (2015); and Ebru (2012). However, the recently conducted study in Apapa jetty and Dadda water by Chukwu and Akinyanmi (2018) reported lower values, suggesting a high concentration of Cu. The high Cu concentration in this study could be attributed to sand mining and dredging activities. The values were, on average, four times lower than 47 mg/kg set by Swedish Environmental Sediments Quality Guideline, SESQG (1996), as presented in Table 4.
Higher values of Fe were found in all three terminals, with Terminal A in the highest concentration (35.625 ± 2.946 mg/kg). Terminal C had the lowest value (30.000 ± 0.884 mg/kg), while the control (Takwa bay) concentration was 6.876 ± 0.010 mg/kg. The low pH value of Terminal C may be accountable for the lowest content of iron in the sediment. This is because a decrease in pH value increases the solubility of many potentially toxic metals such as Al, Hg, Mn, and Fe (Sintorini et al. 2021). Iron is a trace element, nutritionally important, and aids metabolic processes. In this study, the iron concentrations were higher than the 4 mg/kg severe effect level by SESQG (1996), as presented in Table 4. This might be attributed to the dredging and landfilling operations by terrestrial sediments.
To safeguard aquatic biota from the detrimental and toxic impacts associated with sediment-bound pollutants, a number of Sediment Quality Guidelines (SQGs) have been developed to assess the degree of potential harm that the chemical state of sediment may cause to aquatic life and are intended to be used in the interpretation of sediment quality. They are also utilized in order to prioritize and rank contaminated areas for further research (Yanhao et al. 2018). Applying the Washington Department of Ecology Sediment Quality Guidelines (WDOE 1995), the Apapa bay is classed as non-polluted with respect to Pb. However, the elevated levels of Cd prompted the classification of the bay as a heavily polluted area. Portuguese legislation classification (attached as supplementary information) of sediment in the coastal zone classified the bay as clean dredge sediment in terms of Cu and trace contaminated sediment in terms of Fe.
Recovery studies
The summary of the results of the spike recovery tests is presented in Table 6, and it was evident from the percentage recoveries of the potentially toxic metals that the uncertainties of the analytical methodologies fell within acceptable limits, thus validating the accuracy of the calibration method employed.
Test of significance: Analysis of variance (ANOVA)
For the correlation analysis (Table 7), there was no significant difference between each terminal (A, C, and D) and that of Takwa Bay in terms of Cd and Cu. However, significant differences exist between all the terminals (A, C, and D) and Takwa Bay for Fe and Pb.
Correlation analysis of potentially toxic metals analyzed
The coefficient of correlation describes the degree of relationship between two continuous variables. Oftentimes, it is scaled in the range –1 through 0 to +1, where -1 indicates a perfect inverse relationship of the two comparing variables; 0 means that there is no linear association, and +1 describes a perfect linear relationship. An important oxide of Fe known as iron (oxyhydr) oxide is readily available in the environment, and due to its high surface areas and reactivity, it greatly influences the retention capacity of potentially toxic metal retention in surface sediment (von der-Heyden and Roychoudhury 2015). Literature reports that co-precipitation of potentially toxic metals in the presence of iron (oxyhydr) oxide is affected by total hardness (Ahn et al. 2018). More so, the solubility of metals, including potentially toxic metals such as Cu, Cd, Mn, and Fe, is inversely governed by the pH of the solution (Sintorini et al. 2021). Therefore, a correlation of the sediment’s iron contents, pH values and total hardness with the sediment's potentially toxic metals were analyzed. As illustrated in Table 7, most of the metals showed a close relationship with Fe. Thus, the results suggested that Fe is important and the cause of the metal enrichment in the sediments. Positive and significant correlation (p < 0.05) among Cd, Fe, Pb, and pH reveals the dependency of these metals on pH. The negative correlation observed for Cu with pH is suggestive of the metal not being associated with pH but can be attributed to other sources. In addition, the correlation matrix shows a significant and positive correlation among Cd, Cu, Fe, and Pb.