The statistical summary of the concentration of the selected trace elements are shown in Table 2 while a discussion on the vulnerability, spatial distribution and health risk assessment are presented in the following paragraphs.
Table 2
statistical summary of the concentration of the trace elements.
Elements | Cu(mg/l) | Fe(mg/l) | Zn(mg/l) | Pb(mg/l) | Mn(mg/l) | Cr(mg/l) |
min | 0.00 | 0.01 | 0.00 | 0.0006 | 0.00 | 0.01 |
max | 5.10 | 2.00 | 3.70 | 0.0100 | 6.05 | 23.00 |
meab | 0.69 | 0.79 | 0.65 | 0.0080 | 0.70 | 2.08 |
median | 1.09 | 1.73 | 0.91 | 0.0086 | 1.18 | 4.44 |
sdev | 1.04 | 0.74 | 0.78 | 0.0006 | 1.09 | 3.98 |
WHO(2011) | 2.00 | 0.05 | 3.00 | 0.0100 | 0.40 | 0.05 |
NSDW(2007) | 1.00 | 0.30 | 3.00 | 0.0100 | 0.20 | 0.05 |
4.1 Vulnerability and Spatial Distribution of the trace elements
4.1.1 Manganese (Mn)
Manganese is one of the most abundant metals in the Earth’s crust, usually occurring with iron, oxygen, sulfur and chlorine ATSDR (2012). Just like iron, Manganese is a redox sensitive element. Although manganese is an essential metal for the body, it recently became a metal of global concern when methyl cyclopentadienyl manganese tricarbonyl (MMT), which was known to be toxic was introduced as a gasoline additive. MMT has been claimed to be an occupational manganese hazard and linked with the development of Parkinson’s disease-like syndrome of tremour, gait disorder, postural instability and cognitive disorder. Exposure to elevated levels of manganese can result in neurotoxicity. Manganism is a neurological disease due to manganese characterized by rigidity, action tremour, a mask-like expression, gait disturbances, bradykinesia, micrographia, memory and cognitive dysfunction, and mood disorder. The symptoms of manganism are very similar to that of Parkinson disease. Liao et al (2018) stated that mineralogical composition of rocks, redox conditions and water flow conditions are the basic factors that influences the concentration of manganese bearing minerals such as Pyrolisite, magamite, braunite and rhodochrosite found in soils and rocks. Some pyroxene bearing minerals and mica group minerals such as montdorite are notable sources of Manganese. The manganese contents in the samples range from 0to 6.05mg/l with an average of 0.619 which is higher that the specified limit by WHO (2011). Also, about 43.3% of the samples fell short of this specification. Afolagboye et al (2015) identified a prominent occurrence of manganese bearing minerals in all the rocks in the study area except quartzites. This is reflected in the meagre occurrence of manganese in water samples from areas underlain by quartzite. Excessive intake of manganese can lead to intellectual impairment and decreased intelligence quotients in school-aged children (Bouchard et al 2011). High manganese concentration are observed in parts of the area (Figure 2a and 2b). However, the highest concentrations are noticed in wells located around the porphyritic granite and charnockite region which are highly enriched in hornblende, biotite and pyroxene which are recognized sources of manganese (Caretero and Kruse, 2015). Spatial maps pf manganese with respect to the world health organization and Nigerian standards are shown in figures 2a and 2b, many of the samples fulfill the WHO(2011) specification than the Nigerian standard.
4.1.2 Chromium (Cr)
In most cases, Chromium (III) compounds and some other species are much less toxic and has little or no health concerns, Chromium in its hexavalent form, is the most toxic species of chromium though problems. A recent work by Madukwe et al (2020) reiterated that Chromium (VI) may be corrosive and also cause allergic reactions to the body. Hence, breathing high levels of chromium (VI) can cause irritation to the lining of the nose and nose ulcers. In addition, it can cause anemia, irritations, ulcer, and sperm damage and impair the male reproductive system. Severe redness and swelling of the skin are also common allergies attributed to chromium (VI). In addition, human exposure to extremely high doses of chromium (VI) compounds can result in severe cardiovascular, respiratory, hematological, gastrointestinal, renal, hepatic and neurological effects and possibly death Engwa et al. (2018). Jardine et al (1999) noted that food appears to be the major source of intake (Robson, 2003). The analyses revealed that chromium range from 0.01-23mg/l with an average of 0.5mg/l. and the main sources of chromium are chromite, chromium bearing magnetite and ilmenite. Also, Chromate found in amphiboles, pyroxenes, biotite, magnetite, olivine and feldspars (Bricker and Jones, 1995). A minimal intake of chromium has been advocated as a result of its carcinogenic nature (WHO, 2011). 61.6% of the analyzed samples recorded concentrations greater than the maximum stipulated by NSDW (2007) and WHO(2011). Figure 2a depicts the spatial distribution of chromium in the study area. It is very clear from the map that most part of the area have concentrations higher than the permissible level recommended by both WHO and the Nigerian regulating body. As such, the populace could be at risk of diseases related to high intakes of chromium as stated above. Areas with extremely high concentrations are in the southern portion and the southwestern part of the study area.
4.1.3 Zinc (Zn)
Zinc is abundant in the earth’s crust. It is a chalcophile metallic element and forms several minerals, including sphalerite (ZnS), the commonest Zn mineral, smithsonite (ZnCO3) and zincite (ZnO), but is also widely dispersed as a trace element in pyroxene, amphibole, mica, garnet and magnetite. Andrews and Sutherland (2004). It is released to the environment from both natural and anthropogenic sources; however, releases from anthropogenic sources are greater than those from natural sources Barbera et al. (1991). Apart from the dissolution of zinc in water, which increases with acidity, zinc is immobile in water Gundersen and Steinnes (2003). Toxicity in human may occur if zinc concentration approaches 400 mg/kg and 3 mg/L in soil and water, respectively. This is characterized by symptoms of irritability, muscular stiffness and pain, loss of appetite and nausea. Zinc appears to have a protective effect against the toxicities of both cadmium and lead Fergusson (1990). Zn has been shown to exert adverse reproductive biochemical, physiological and behavioral effects on a variety of aquatic organisms as concentrations exceed 20 mg/kg. Toxicity is, however, influenced by many factors such as the temperature, hardness and pH of the water WHO (2011). WHO (2011) expects drinking water to contain a maximum zinc concentration of 3mg/l. it has the ability to form soluble compounds at neutral and acidic pH. Therefore it is among the most mobile heavy metals in groundwater (Malecki et al, 2017). It is used as an agent to protect iron pipelines against corrosion which may contaminate groundwater due to oxidation. Zinc naturally occurs in sphalerite, smithsonite, hemimporphite, wurtzite and hydrozincite (Emsley, 2001). Biotite is a notable carrier of zinc in granite (Ure and Berrow, (1982). It is important to state that zinc may be linked to an organic precursor derived from limestone or coral reefs. Khatri and Tyagi (2015) stressed that zinc is not related to a particular bedrock type due to its adsorption to iron hydroxides and anthropogenic sources from agrochemicals and residential areas. The groundwater samples recorded zinc content as ranging from 0.001-3.7 and a mean value of 0.603. The average value is lower than the maximum value specified by WHO (2011) and the NSDW (2007) with only on sample exceeding both standards. Zinc does not show critical variations within the study area as value notably fell below the total limiting value specified by NSDW(2007) and WHO(2011) except one of the samples from the well locations. This well is underlain by a biotite granite. Biotite which has been recognized as a main zinc carrier (Embaby and Redwan, 2019). Therefore the enrichment at this particular location can be attributed to the weathering of this rock.
4.1.4 Lead (Pb)
The general population is exposed to lead from air and food in roughly equal proportions. Its occurrence and concentrations in drinking water is generally below 5 mg/L, although much higher concentrations (above 100 mg/L) have been measured where lead fittings are present Howard and Bartram (2003). Owing to the decreasing use of lead-containing additives in petrol and of lead-containing solder in the food processing industry, concentrations in air and food are declining, and intake from drinking water constitutes a greater proportion of total intake of lead Sawyer et al. (1998). Lead is a highly toxic metal whose widespread use has caused extensive environmental contamination and health problems in many parts of the world. The common symptom of contamination of lead is lead poisoning which displays as anemia because lead interferes with the formation of hemoglobin. It prevents iron uptake. Higher levels of lead may produce permanent brain damage and kidney dysfunction.Engwa et al. (2018) noted that among others acute exposure of lead can cause loss of appetite, fatigue, sleeplessness, hallucinations, vertigo, renal dysfunction, hypertension and arthritis, while chronic exposure can result in birth defects, mental retardation, autism, psychosis, allergies, paralysis, weight loss, dyslexia, hyperactivity, muscular weakness, kidney damage, brain damage, coma and may even cause death. The presence of the lead in natural water is largely linked to lead bearing minerals such as galena, and Cerissite (Liao et al 2018; Lu et al, 2018). Lead values range between 0.008 and 0.01, none of the water samples have concentrations higher than the limit specified by (NSDW, 2007) and WHO (2011). On the average, wells located within areas underlain by porphyritic granite have the highest lead concentration while those within the charnokites and quartzites recorded least mean values. The intake of lead results in tiredness, anemia, irritability behavior changes and impairment of intellectual functions (Tebbubt, 1983). It is also interesting that the lead concentration falls within the limiting values of the NSDW (2007) and WHO (2011).
4.1.5 Iron (Fe)
Iron is a redox sensitive element which exhibit a high solubility at low pH. The main sources of iron in natural water are iron oxide and hydroxide minerals such as hematite, limonite, magnetite, pyrite, siderite and iron silicate. They are prominent in amphiboles, pyroxenes and micas. Iron values range between 0.006 and 2µg/l with a mean of 0.7841 and based on the mean the order of abundance with respect to the bedrock is as follows: porphyritic granite>Charnokite>Migmatite > Quartzite. This is a reflection of the influence of the mineralogy of the host rock of the wells on the chemistry of the groundwater as the rocks with higher average values are very rich in iron bearing minerals such as pyroxene, mica and amphibole (Afolagboye et al, 2015). Excessive ingestion of iron can lead to life threatening conditions such as liver disease, heart problems and diabetes. Also, high occurrence of iron concentration produces rusty hydroxides in the wells and may cause staining in laundry and undesirable taste in beverages (Daramola, 2013). It is important to note that iron concentrations in areas underlain by basement rocks are usually less thann 1mg/l and rarely exceeds 2mg/l (Daramola, 2013), the results of this study is consistent as the iron concentration in the samples are well below these values. The concentrations of iron is higher than the global limit in majority of the study area (figure….). Hence, the inhabitants are at the risk of the ailments related to excessive intake of iron. Also, some unpleasant metallic taste, rust colored stains in laundry and rough and scaly skins. The spatial maps based on the Nigerian specification indicates that areas that exceed the limits stipulated are slightly higher than that of the world health organization. The WHO (2011) specified a maximum concentration of 2mg/l for copper in drinking water. Copper occurrence in groundwater are usually attributed to copper sulphides such as chalcopyrite, chalcocite, copper carbonates, malachites etc (Mapoma et al , 2017). The concentration of copper in the water samples range between 0.002 and 5.1mg/l. only 8.3% exceed the WHO(2011) standard while 30% of the samples exceed the NSDW (2007) specification. Embaby and Redwan (2019) stated that higher copper concentration in water samples from wells in a granitic terrain reflects an alteration of copper bearing minerals. Although, despite the benefits of copper to human health, a higher concentration may cause neurological disorder, hypertension, liver and kidney dysfunction (Ahmed, et al , 2018, Obasi and Akudinobi, 2020). The spatial distribution maps for copper indicates that the concentrations are higher only in few pockets of places running from south to the northern parts of the area. However, most of the sampled wells recorded concentrations lower than the maximum permissible value recommended the Nigerian regulating body as compared with the WHO(2011) standards as shown in the spatial distribution maps (figure 2c and d).