Egypt faces a rapidly increasing deterioration of its surface and groundwater due to the discharges of industrial effluents and domestic wastes into its waterways, which contain harmful or poisonous substances. The excessive application of fertilizers and pesticides in agriculture also causes water pollution problems. Contamination of water caused by different effluent discharges could probably be hazardous to human health (Wahaab & Badawy 2004; Al-Afify et al. 2018).
The Nile River constitutes the main water resource of Egypt. The Nile River in the Cairo region supplies water to a population of approximately 15 million people and supports many commercial and industrial activities. Heavy industry is located around North and South Cairo, in addition to some heavy and small industries located randomly throughout the city.
Water pollution is one of the serious environmental problems resulting from urbanization, overpopulation and industrialization, in addition to ignorance (Narain et al. 2011). A large discharge of heavy metals into the aquatic environment eventually accumulates in water, sediments and dependent biotic components like fish and aquatic plants (Rybak et al. 2013). Heavy metals are of particular concern because of their characteristics such as toxicity, abundance, ubiquity, bioaccumulation capacity and resistance to decomposition. These compounds do not degrade and therefore accumulate in bodies of organisms or sediments, and can pose a significant threat to the health of humans and other plants, animals and ecosystems (Alahabadi & Malvandi 2018). Water contamination with heavy metals is therefore a serious concern in today’s world (Miretzky et al. 2004).
Rivers receive sediment from several diffuse and point sources, which is deposited at the bottom and acts as potential sources of metal accumulation in the aquatic food chain through the biomagnification process (Singh et al. 2017). Sediments are considered a sink and reservoir of many toxic contaminants, including heavy metals, and have been used to assess the historical pollution status (Thevenon et al. 2011). Heavy metals can be stored in sediment for a short period of time, where some of these fixed heavy metals may be released into the overlying water and taken up by the aquatic biota (Singh et al. 2017). Many factors, such as temperature, pH and dissolved oxygen levels in water, control the fate of metals through sorption, precipitation and dissolution processes (Duncan et al. 2018).
Aquatic plants play an important role in sequestering large quantities of nutrients and metals from the environment by storing them in the roots and/or shoots. Aquatic plants have high remediation potential for macronutrients due to their general fast growth and high biomass production (Shaltout et al. 2009). Macrophytes are important in the biological monitoring of aquatic ecosystems, because changes in the composition of aquatic vegetation are considered a reliable biological indicator of the water quality. Many studies have researched the use of macrophytes as indicators of bioaccumulation of metals (Pajević et al. 2002; Prasad & Freitas 2003; Vardanyan & Ingole 2006). However, while macrophytes are useful biomonitors, the bioconcentration of metals in macrophytes may result from exposure to metals in both water and/or sediments, making it difficult to directly compare between the concentrations measured in plants and in the environment (i.e. water or sediments).
Unusually high inputs of metals into the aquatic environment have resulted in great financial losses, affected commercial fisheries and in some cases have been hazardous to human health (Banerjee 2003). Research on heavy metals in aquatic environments has become very important due to concerns over accumulation and toxic effects in aquatic organisms and humans through the food chain (Alahabadi & Malvandi 2018).
The most important objectives of this study include: (a) determination of the distribution and concentration of Fe, Mn, Ni, Co, Zn, Cu, Cr Pb and Cd in the water, sediment and macrophytes (
The Nile is the main source of fresh water in Egypt; its flow rate relies on the available water stored in Lake Nasser to meet the needs defined under the annual water budget of Egypt (Agricultural Policy Reform Program 2002). The Nile River enters Egypt at its southern border with Sudan and runs through a narrow valley (1000 km long) whose width varies from 2 to 20 km. Nile pollutants are derived from different uncontrolled sources such as agricultural drainage, industrial wastewater and municipal wastewater. The river in the Cairo region receives heavy polluted, treated or partially/untreated industrial drainage water, containing waste from the iron, cement, and sugar industry in the Helwan area. These types of industry tend to pollute the Nile system with heavy metals, suspended matter and organic micropollutants. The main characteristics of the Nile water in the Cairo region are presented in Table 1 and the sampling sites are presented in Figure 1.
Map of the Nile River showing the sampling sites (after Al-Afify et al. 2018)
Main characteristics* of the Nile River water in the Cairo region
Variable | Range | Mean ± SD |
---|---|---|
Transparency (cm) | 35–150 | 86.97 ± 25.63 |
Depth (m) | 1–10 | 4.02 ± 0.82 |
Dissolved oxygen (DO) (mg l−1) | 4.0–10.26 | 8.02 ± 1.36 |
pH | 7.32–8.81 | 8.02 ± 0.30 |
Alkalinity (mg l−1) | 92.0–186.5 | 135.8 ± 25.98 |
Chloride ion (mg l−1) | 11.0–88.97 | 48.51 ± 21.35 |
*cited after Al-Afify et al. (2018)
Subsurface (about 30 cm) water samples were collected using a polyvinyl Van Dorn plastic bottle. Samples were kept in clean stoppered plastic bottles and preserved with 65% HNO3 to pH <2. Finally, water samples were digested using 65% HNO3 according to APHA (2005).
Sediment samples were collected using an Eckman sampling device from the top 20 cm layer of the bottom at eight sampling sites in the Nile River in the Cairo region. Samples were air-dried and stone fragments were removed by passing the dried samples through a 2 mm sieve. The sieved samples were powdered and 0.5 g of finely ground samples was digested according to the method described by Kouadia and Trefry (1987).
Representative macrophytes were sampled at each site according to the type of plant (submerged or floating). The floating macrophyte (
Plants were rinsed thoroughly with distilled water (four times) and dried at 60°C until completely dry. The dried plant parts were ground and precise weigh (0.50 gram) of each sample was digested using 65% HNO3, 98% H2SO4 and 35% H2O2 as prescribed by Saison et al. (2004).
Samples (water, sediment and macrophytes) were analyzed for Fe, Mn, Ni, Co, Zn, Cu, Cr Pb and Cd concentrations using an atomic absorption reader (Savant AA-AAS with graphite furnace; GF 5000). The precision of metal analysis was controlled by triplicate readings and the mean value was determined with relative standard deviations below 5%.
The suitability of Nile water for the drinking purpose with respect to metals was determined using the heavy metal pollution index
where
While
where
The geoaccumulation index
The
where
Geoaccumulation index (
Index | ||||||
---|---|---|---|---|---|---|
Geoaccumulation index ( |
Enrichment factor ( |
Modified contamination degree ( |
||||
Class no. | Contamination level | Contamination level | Contamination level | |||
0 | practically unpolluted | 1 < |
minor enrichment | nil pollution | ||
1 | 0 < |
unpolluted to moderately polluted | 3 < |
moderate enrichment | 1.5 ≤ |
low pollution |
2 | 1 < |
moderately polluted | 5 < |
moderately severe enrichment | 2 ≤ |
moderate pollution |
3 | 2 < |
moderately to heavily polluted | 10 < |
severe enrichment | 4 ≤ |
high pollution |
4 | 3 < |
heavily polluted | 25 < |
very severe enrichment | 8 ≤ |
very high pollution |
5 | 4 < |
heavily to extremely polluted | ultra-high | 16 ≤ |
extremely high pollution | |
6 | extremely polluted | ultra-high pollution |
The
Fe was used as a conservative tracer to differentiate natural from anthropogenic components. (
where
where a
The
where
The potential ecological risk index (
and
where
The ability of plants to absorb and accumulate metals from the aqueous growth media was assessed using the bioconcentration factor (
Correlations among metal concentrations in water, plants and sediment samples were estimated using Pearson correlation coefficients (
Pollution levels according to ER and
Ecological risk levels for single factor pollution | Potential ecological risk levels | ||
---|---|---|---|
Low | Low grade | ||
40 ≤ |
Moderate | 150 ≤ |
Moderate |
80 ≤ |
Considerable | 300≤ |
Severe |
160 ≤ |
High | 600 ≤ |
Serious |
320 ≤ |
Serious | - |
Table 4 summarizes the range, mean concentrations and standard deviation of Fe, Mn, Ni, Co, Zn, Cu, Cr, Pb, and Cd in river water in different seasons. At most sites, the concentrations of Fe, Cu, Zn, Pb, Co and Cd in different seasons were higher than the CCME (2007) threshold limits established to protect water quality for aquatic life. Pb and Cd concentrations in the Nile water were several times higher than the limits recommended by CCME (2007), where cadmium has lethal effects on aquatic biota such as crustaceans (Effendi et al. 2016). Ni is the only metal whose concentration in water is still at a safe level for aquatic life according to CCME (2007) limits.
Seasonal variation of heavy metals (μg l−1) compared with different criteria and HPI values in the Nile water in the Cairo region
Autumn | Winter | Spring | Summer | CCME (2007) | WHO (2011) | EWQS (2007) | ||
---|---|---|---|---|---|---|---|---|
Fe | Range | 642.0–1090.0 | 775.0–1300.0 | 403.0–862.0 | 196.0–690.0 | 300 | 1000 | 300 |
Mean±SD | 869.0±169.6 | 1005.8±166.4 | 566.6±142.7 | 433.25±165.13 | ||||
Mn | Range | 97.81–234.81 | 96.46–287.68 | 90.79–161.5 | 87.33–121.24 | - | 400 | 100 |
Mean±SD | 152.2±44.7 | 191.7±61.9 | 124.9±25.0 | 97.9±10.5 | ||||
Ni | Range | 9.54–20.54 | 11.89–26.47 | 9.04–25.41 | 8.45–17.68 | 65 | 70 | 20 |
Mean±SD | 12.79±3.87 | 16.51±5.32 | 16.48±5.78 | 11.94±3.19 | ||||
Co | Range | 4.85–20.54 | 6.95–22.63 | 9.51–24.35 | 8.45–21.35 | 1 | - | - |
Mean±SD | 13.45±5.30 | 14.75±5.30 | 16.39±5.85 | 13.99±4.83 | ||||
Zn | Range | 22.56–75.48 | 28.91–98.56 | 24.35–36.55 | 18.34–42.18 | 30 | 4000 | 3000 |
Mean±SD | 38.97±17.34 | 38.97±17.34 | 31.74±4.58 | 29.87±9.49 | ||||
Cu | Range | 6.45–18.40 | 6.15–19.42 | 7.05–14.12 | 5.12–9.45 | 2 | 2000 | 2000 |
Mean±SD | 11.71±4.14 | 10.44±4.48 | 10.65±3.10 | 7.47±1.38 | ||||
Cr | Range | 9.47–17.96 | 8.79–20.68 | 10.69–21.34 | 9.75–16.58 | - | 50 | 50 |
Mean±SD | 12.28±3.03 | 13.99±3.72 | 14.24±3.84 | 12.42±2.12 | ||||
Pb | Range | 5.75–12.45 | 4.15–12.15 | 4.01–9.85 | 3.15–18.47 | 2 | 10 | 10 |
Mean±SD | 9.18±2.18 | 7.26±2.72 | 6.13±1.89 | 9.65±5.60 | ||||
Cd | Range | 1.98–2.98 | 1.45–2.98 | 1.75–3.15 | 1.98–3.84 | 0.18 according to CCME (2014) |
3 | 3 |
Mean±SD | 2.35±0.37 | 2.26±0.54 | 2.40±0.55 | 2.79±0.69 | ||||
HPI according to WHO (2011); |
Range | 61.3–96.3 | 46.8–88.7 | 56.6–96.7 | 64.3–104.2 | |||
HPI according to EWQS (2007); |
Range | 64.3–99.0 | 53.3–90.4 | 64.3–96.7 | 66.4–104.1 |
The calculated ranges of
Concerning the metal pollution, the Nile water in Cairo can be categorized as having a low level of metal pollution (Cd < 1), except site 4 in the winter season (low flow) when water is moderately polluted by metals (Cd ≤ 3) according to EWQS (2007) limits (Fig. 2). Therefore, severe precautions at the anthropogenic input sites should be taken to control the influx of elements.
Contamination index values (
The concentrations of heavy metals in sediment from different sites at the Nile River are presented in Table 5. As shown in Tables 4 and 5, the levels of heavy metals in the Nile sediment were much higher than those in water and showed enrichment with metals in the Nile sediment.
Heavy metals distribution (μg g−1) compared with EPA (2006), contamination factor (
Metal | Autumn | Winter | Spring | Summer | EPA (2006) | ||
---|---|---|---|---|---|---|---|
Fe | Range | 27154–53468 | 18238–25014 | 17548–26481 | 17185–25678 | 20000 | 0.86–2.67 |
Mean±SD | 38858 ± 9784 | 22774 ± 2166 | 21121 ± 2878 | 19217 ± 2862 | 1.27±0.47 | ||
Mn | Range | 283.0–1334.0 | 339.0–988.0 | 273.0–456.0 | 512.0–984.0 | 460 | 0.59–2.90 |
Mean±SD | 849.3 ± 354.4 | 708.0 ± 215.2 | 326.8 ± 58.5 | 754.4 ± 174.4 | 1.43±0.64 | ||
Zn | Range | 45.00–122.45 | 58.70–120.00 | 46.32–70.00 | 62.40–97.50 | 121 | 0.37–1.01 |
Mean±SD | 84.44 ± 27.82 | 77.34 ± 19.69 | 60.06 ± 8.54 | 83.66 ± 12.05 | 0.63±0.17 | ||
Cu | Range | 18.70–30.45 | 19.50–27.89 | 19.85–25.91 | 10.80–20.15 | 31.6 | 0.34–0.96 |
Mean±SD | 25.49 ± 4.24 | 23.61 ± 2.77 | 22.58 ± 2.20 | 14.31 ± 3.22 | 0.68±0.17 | ||
Ni | Range | 28.38–87.12 | 27.95–80.52 | 24.75–72.85 | 32.52–67.85 | 22.7 | 1.09–3.84 |
Mean±SD | 50.44 ± 20.19 | 50.94 ± 19.39 | 47.94 ± 16.75 | 45.06 ± 13.23 | 2.14±0.74 | ||
Co | Range | 7.19–19.50 | 7.40–20.45 | 5.40–17.85 | 7.56–17.64 | 50 | 0.11–0.41 |
Mean±SD | 13.06 ± 4.11 | 12.95 ± 4.92 | 11.20 ± 4.00 | 11.27 ± 3.65 | 0.24±0.08 | ||
Cr | Range | 16.85–54.65 | 18.96–52.56 | 13.67–48.97 | 14.52–47.52 | 43.4 | 0.31–1.26 |
Mean±SD | 25.27 ± 12.83 | 28.11 ± 12.93 | 26.85 ± 11.37 | 25.44 ± 11.23 | 0.61±0.27 | ||
Pb | Range | 6.52–18.41 | 9.50–25.12 | 10.00–30.33 | 5.86–11.50 | 35.8 | 0.16–0.85 |
Mean±SD | 12.12 ± 4.23 | 16.82 ± 4.47 | 18.83 ± 8.18 | 7.85 ± 1.83 | 0.39±0.18 | ||
Cd | Range | 2.05–3.19 | 1.74–3.21 | 1.86–3.42 | 2.14–3.24 | 0.99 | 1.76–3.45 |
Mean±SD | 2.75 ± 0.45 | 2.51 ± 0.53 | 2.74 ± 0.50 | 2.62 ± 0.40 | 2.68±0.46 | ||
PLI | Range | 0.76–1.08 | 0.72–1.05 | 0.73–0.97 | 0.56–0.73 |
There is a significant difference between the seasons (
The average concentrations of heavy metals in sediments were in descending order: Fe > Mn > Zn > Ni > Cr > Cu > Pb ≈ Co > Cd. The high level of Cr recorded at site 4 (54.65, 52.56, 48.97 and 47.52 mgkg−1 in autumn, winter, spring and summer, respectively), exceeding the freshwater sediment EPA benchmarks, indicates its higher input, which may originate from urban and industrial waste (Mohiuddin et al. 2012).
For most sites, especially during the low flow seasons, the concentrations of Mn, and Ni were higher than the freshwater sediment benchmarks of EPA (2006). However, the levels of Cd were significantly higher than the benchmarks for all sites in different seasons.
Pearson’s correlation matrix for the analyzed sediment elements showed a significant positive correlation between Ni, Co and Cr (Table 6), suggesting similar sources of input (human or natural) for these elements in the Nile River sediment. High correlations between the same elements (Ni, Co and Cr) in water (Table 6) may reflect similar levels of contamination or/and release from the same sources of pollution, identical behavior during their transport in the Nile system and mutual interactions (Ali et al. 2016; Abdel-Satar et al. 2017).
Correlation between the elements in water and sediments of the Nile River in the Cairo region
Water | |||||||||
---|---|---|---|---|---|---|---|---|---|
Fe | Mn | Zn | Cu | Ni | Co | Pb | Cd | Cr | |
Fe | 1.00 | ||||||||
Mn | −0.02 | 1.00 | |||||||
Zn | −0.30 | −0.24 | 1.00 | ||||||
Cu | 0.20 | 0.05 | 0.19 | 1.00 | |||||
Ni | −0.13 | 0.23 | 0.07 | −0.20 | 1.00 | ||||
Co | −0.29 | 0.13 | 0.27 | −0.09 | 0.75 *Correlation is significant at |
1.00 | |||
Pb | 0.17 | 0.07 | 0.14 | 0.66 *Correlation is significant at |
−0.46 | −0.40 | 1.00 | ||
Cd | −0.06 | −0.06 | 0.09 | −0.01 | −0.02 | 0.12 | −0.11 | 1.00 | |
Cr | −0.20 | 0.15 | 0.19 | −0.21 | 0.83 *Correlation is significant at |
0.73 *Correlation is significant at |
−0.41 | 0.15 | 1.00 |
Sediment | |||||||||
---|---|---|---|---|---|---|---|---|---|
Fe | 1.00 | ||||||||
Mn | 0.52 | 1.00 | |||||||
Zn | 0.14 | 0.34 | 1.00 | ||||||
Cu | 0.53 *Correlation is significant at |
0.16 | 0.06 | 1.00 | |||||
Ni | 0.18 | −0.08 | −0.20 | −0.23 | 1.00 | ||||
Co | 0.10 | −0.15 | −0.09 | −0.20 | 0.84 *Correlation is significant at |
1.00 | |||
Pb | −0.04 | −0.18 | −0.32 | 0.54 *Correlation is significant at |
−0.35 | −0.47 | 1.00 | ||
Cd | 0.01 | −0.24 | −0.03 | −0.05 | 0.29 | 0.48 *Correlation is significant at |
−0.24 | 1.00 | |
Cr | −0.01 | −0.13 | −0.16 | −0.20 | 0.85 *Correlation is significant at |
0.81 *Correlation is significant at |
−0.36 | 0.33 | 1.00 |
The results of the
The enrichment factor (
Enrichment factor for the studied elements in the Nile River in the Cairo region
Mn | Zn | Cu | Ni | Co | Pb | Cr | Cd | ||
---|---|---|---|---|---|---|---|---|---|
Autumn | Range | 0.35–1.54 | 0.17–0.70 | 0.33–0.65 | 0.78–1.96 | 0.06–0.22 | 0.10–0.38 | 0.15–0.57 | 0.87–2.21 |
Mean±SD | 0.95±0.34 | 0.38±0.17 | 0.43±0.11 | 1.22±0.47 | 0.14±0.06 | 0.18±0.09 | 0.31±0.14 | 1.54±0.57 | |
Winter | Range | 0.66–1.82 | 0.44–0.88 | 0.55–0.79 | 1.15–3.03 | 0.13–0.34 | 0.23–0.76 | 0.34–0.99 | 1.76–2.81 |
Mean±SD | 1.34±0.36 | 0.56±0.15 | 0.65±0.09 | 2.03±0.74 | 0.23±0.08 | 0.46±0.20 | 0.56±0.23 | 2.22±0.42 | |
Spring | Range | 1.16–2.21 | 0.49–0.91 | 0.53–0.81 | 1.18–2.95 | 0.11–0.35 | 0.23–0.73 | 0.32–0.97 | 2.02–3.35 |
Mean±SD | 1.57±0.38 | 0.66±0.16 | 0.68±0.11 | 2.06±0.68 | 0.21±0.08 | 0.46±0.18 | 0.58±0.22 | 2.64±0.57 | |
Summer | Range | 0.58–1.14 | 0.43–0.66 | 0.30–0.73 | 1.44–3.16 | 0.15–0.37 | 0.13–0.37 | 0.29–1.10 | 2.05–3.42 |
Mean±SD | 0.75±0.16 | 0.52±0.07 | 0.48±0.15 | 2.15±0.61 | 0.24±0.08 | 0.23±0.07 | 0.61±0.27 | 2.79±0.47 |
Another index to assess the contamination of elements in the Nile River sediments in the Cairo region is the pollution load index. The resulting
The average potential ecological risk (ER) was categorized as low-grade risk (ER < 150), viewed from the overall perspective of the study (Fig. 5). The contribution of Cd to the ecological risk assessment was about 80%, while the contribution of Ni was about 10%. The contribution of the other six investigated metals was as follows: Mn – 1.5%, Zn – 0.6%, Cu – 3.5%, Co – 0.5%, Pb – 2.0% and Cr – 1.2%. Consequently, Cd contained in the Nile sediment surface may have a significant ecological effect. Based on the monomial ecological risk index (
Mn | Zn | Cu | Ni | Co | Pb | Cd | Cr | |
---|---|---|---|---|---|---|---|---|
Min. | 0.59 | 0.37 | 1.71 | 5.45 | 0.22 | 0.82 | 52.73 | 0.63 |
Max | 2.90 | 1.01 | 4.82 | 19.19 | 0.82 | 4.24 | 103.64 | 2.52 |
Contribution (%) | 1.5 | 0.6 | 3.5 | 10.7 | 0.5 | 2.0 | 80.0 | 1.2 |
Concentrations of the metals in the two plants from the Nile River are listed in Figure 6. The distribution of most studied elements between water, sediment and plants at different sites showed a similar trend: sediment >plants >water. Fe was the most frequently accumulated metal in the two plants, followed by Mn, Zn, Cu, Ni, Co, Cr and Pb, whereas Cd was the least frequently accumulated one. The results show a significant increase in the level of most of the studied metals in
Average distribution of metals in
Average BCF in
There were differences in the sequences of the studied metal levels in the macrophytes compared to the sequences of their bioaccumulation ability. These differences indicate a different capacity of macrophytes for different metals (Kastratovi et al. 2014). Factors involved in the identification of such differences include ionic exchange, the rate of chelation, translocation of element ions, chemical precipitation and precipitation induced by microorganisms or by root exudates (Pajević et al. 2008).
The distribution of most studied metals between water, sediment and plants at different sites showed a similar trend: sediment > plants > water. Pb and Cd concentrations in the Nile water were several times higher than CCME recommended limits, while Ni is the only metal whose concentration in water is still at a safe level for aquatic life. The Nile water in Cairo is not critically polluted by the studied metals and the HPI and the contamination index for most sites do not exceed the critical limit according to WHO and EWQS.
The geoaccumulation index (
The BCF values for metals were ranked as follows: Cu > Mn > Fe > Ni > Co > Zn > Pb ≈ Cr > Cd and Mn > Cu > Fe > Ni > Pb ≈ Zn > Cr ≈ Co > Cd in