3.2 Scope of heavy metals research in Nigeria
3.2.1 Heavy metals in cosmetics and personal care products (PCP)
Manufacturers of cosmetics and skin care products often incorporate substances that could impart substantial amount of heavy metals onto the products. Relevant items to which such substances are incorporated include lip sticks, body creams, sunscreen products, talcum and brown powder, eye shadow, shampoos and concealers. For example, zinc (as the oxide) is widely used in sunscreens, diaper ointments, moisturizers, shampoos and concealers; chromium is used in some products as a colorant; and iron oxides are commonly used as colorants in eye shadows, blushes and concealers (Odukudu et al., 2014). Despite the prohibition of Pb, As, Cd, Co, Sb, Hg, Ni and Cr in cosmetics, many producers still include compounds that contain these metals at levels above
Table 1
Available studies reviewed based on Nigerian geo-political zones
Zone | Number of articles | Metals reported | References |
---|
North-east | 5 | Pb, Cr, As, Cd, Fe and Zn | Amadi et al., 2020; Nduka et al., 2020; Lawal et al., 2021; Usman et al., 2021; Akan et al., 2014 |
North-west | 7 | Ti, Fe, Nb, Pb, Rb, Sr, Y, Cu, Cd, Cr, Ni, Mo, Mn, Zn and Zr | Haruna et al., 2009; Abdu et al., 2011; Tukura et al., 2011; Gaya and Ikechukwu, 2016; Amadi et al., 2020; Datti and Mukhtar, 2020; Usman et al., 2021 |
North-central | 18 | Zn, Pb, Cr, Cu, Fe, Rb, Zr, Ni, Cd, Co, As, Mn | Adekola et al., 2001; Barau et al., 2018; Opaluwa et al., 2012; Mafuyai et al., 2014; Amoo et al., 2005; Isinkaye, 2018; Ramadan and Haruna, 2019; Abalaka et al., 2020; Amadi et al., 2020; Ayua et al., 2020; Emurotu, 2020; Olutona and Daniel, 2020; Orosun et al., 2020; Abdulraheem et al., 2021; Denkok et al., 2021; Oluwasola et al., 2021; Samuel and Babatunde, 2021; Usman et al., 2021 |
South-south | 38 | Cd, Cr, Fe, Zn, Ni, Cu, Pb, Co, Mn, V, Cu | Osuji and Onojake, 2004; Hart et al., 2005; Akaninwor et al., 2006; Wegwu and Akaninwor, 2006; Wegwu and Wigwe, 2006; Iwegbue et al., 2007; Obasohan and Eguavoen, 2008; Iwegbue, 2010; Wegwu and Omeodu, 2010; Iwegbue et al., 2012; Udousoro et al., 2013; Vincent-Akpu and Babatunde, 2013; Amos-Tautau and Onigbinde, 2014; Bassey et al., 2014; Iwegbue et al., 2014; Adebiyi and Adebiyi, 2015; Ebong et al., 2015; Adams et al., 2016; Benson et al., 2016; Anani and Olomukoro, 2017; Omole, 2017; Anani and Olomukoro, 2018; Ebong et al., 2018; Enuneku et al., 2018; Aigberua and Izah, 2019; Ebong et al., 2019; Kalagbor et al., 2019; Aigberua et al., 2020; Amadi et al., 2020; Izah and Aigberua, 2020; Ohiagu et al., 2020; Akinlua et al., 2021; Odigie and Olomukoro, 2021; Ogamba et al., 2021; Usman et al., 2021; Uwah et al., 2021; Uzoekwe et al., 2021; Nwaichi et al., 2016 |
South-east | 31 | Pb, As, Cr, Cd, Hg, Fe, Zn, Cu, Ni, Se, Co, I | Wegwu and Wigwe, 2006; Olife et al., 2007; Obasohan, 2008; Ekere and Ukoha, 2013; Ezeh and Chukwu, 2011; Ekere et al., 2014; Ekwere et al., 2014; Emereibeole et al., 2017; Anyanwu and onyele, 2018; Azi et al., 2018; Ekwere, 2019; Ibe et al., 2018; Ugochukwu, 2019; Verla et al., 2019; Amadi et al., 2020; Anyanwu et al. 2020; Anukwuorji, 2020; Anyanwu and Nwachukwu, 2020; Eze et al., 2020; Obasi and Akudinobi, 2020; Verla et al., 2020; Duru et al., 2021; Eneh, 2021; Njoga et al., 2021; Nnamonu et al., 2021; Omeka and Igwe, 2021; Orji et al., 2021; Ugochukwu et al., 2021; Ugwu and Ofomatah, 2021; Ugbede et al., 2021; Usman et al., 2021 |
South-west | 49 | Cd, Co, Cu, Ni, Pb, Zn, Fe, Cr, Mn, Ti, Fe, Ga, As, Rb, Sr, Se, Zr, Nb, V, Sc | Adekola et al., 2001; Olabanji and Adeniyi, 2005; Wegwu and Wigwe, 2006; Otitoloju et al., 2007; Aiyesanmi et al., 2010; Aiyesanmi and Idowu, 2012; Olutona et al., 2012; Olutona et al., 2013; Odebunmi et al., 2014; Odukudu et al., 2014; Ofudje et al., 2014; Olutona et al., 2014; Tomori and Onibon, 2015; Onojake et al., 2016; Anake et al., 2017; Oguguah and Ikegwu, 2017; Ogundele et al., 2017; Oyebamiji et al., 2018; Aduwo and Adeniyi, 2018; Afolayan, 2018; Olutona and Livingstone, 2018; Maduawuchi et al., 2019; Ogundele et al., 2019; Olutona and Aderemi, 2019; Adebiyi and Ore, 2020; Aiyesanmi et al., 2020; Amadi et al., 2020; Amusan and Adu, 2020; Laniyan and Adewunmi, 2020; Ogundele et al., 2020; Olutona and Daniel, 2020; Achi et al., 2021; Adeyemi and Ojekunle, 2021; Ayodele et al., 2021; Ganiyu et al., 2021; Idowu et al., 2020; Nnaneme, 2021; Ogundele et al., 2021; Olaniyi and Popoola, 2021; Olatunde et al., 2020; Olayinka-Olagunju et al., 2021; Oloruntoba et al., 2021; Olutona et al., 2021; Omokpariola and Omokpariola, 2021; Oyekunle et al., 2021; Oyetibo et al., 2021; Taiwo et al., 2021; Usikalu et al., 2021; Usman et al, 2021 |
the WHO permissible limits. Usman et al. (2021) determined concentrations of Pb, Co, Cu, Cr and Ni on various kinds of cosmetic products in Nigeria and found high concentrations of Co and Pb in face powders and eye shadows, respectively. The study also found that the concentrations of Cr in eyeshadow, lipstick and face powders were above the USEPA and USFDA permissible limits. Eneh (2021) analysed urine samples of female students in a selected Nigerian population to assess impacts of the use of cosmetics on trace metals absorption into the body. The study found that the mean concentration of Hg, Pb and As in the urine of students who had consistently used make-up were higher than those who did not wear make-ups.
Odukudu et al. (2014) investigated the concentration of heavy metals in toothpaste, cosmetics, tissue papers and hair relaxers. Cd and Cr, which are not permitted to be used in personal care products, were present at high concentrations up to 0.467 and 0.435 µg/g (or ppm), respectively, in the products. Despite the fact that Zn is an essential element, the study reported values for Zn that raise safety concerns due to potential cumulative dermal exposure to such high concentrations of the metal. Oyekunle et al (2021) worked on native black soaps and conventional soaps, and reported high Hg concentrations of 273.6 and 55.12 µg/g maximum values, respectively, in the soaps. While noting that highly mercuric soaps are effective against fungi and bacteria, the authors cautioned that such products would only be safe if restricted to occasional use by adults and children. Cd, another very toxic metal, was also detected in the soaps, although at much lower concentrations compared to those of Hg.
3.2.2 Heavy metals in the atmosphere
Heavy metals presence in atmospheric air may result from combustion of fossil fuel. They could also emanate from non-exhaust sources like wear and tear of vehicle brakes and tyres, and from a host of other anthropogenic activities (Anake et al., 2017). Metals may exist in form of vapour in the air, thereby increasing the chance of being inhaled by humans. Studies which investigated toxic metals in air in Nigeria have done so relative to metals bound to particulate matters (PM). Uzoekwe et al. (2021) investigated heavy metals presence and levels in particulate matters (PM10) suspended in air around a gas flaring facility in Bayelsa state. Maximum concentrations of the metals were 0.197, 0.060, 1.280, 0.170, 0.310 and 8.233 µg/m3 for Co, As, Cr, Cd, Cu and Fe, respectively. The study concluded that gas production and flaring did not contribute significantly to atmospheric metal loads within the study area. On the other hand, Anake et al. (2017) determined PM2.5 – bound trace metals in an industrial estate in Ogun state and reported inhalation exposure cancer risks for adults and children, that were well above the acceptable range of 10− 6 to 10− 4, indicating significant contribution of the industrial activities to the levels of suspended metals in air. The study also reported that Cu and Cr exist in the exchangeable form and would be readily transferred to the human system if the particulate matters were inhaled. Ogundele et al. (2017) investigated nine heavy metals (Pb, Mn, Cd, Zn, Cr, As, Ni, Cu, and Fe) in air PM around iron and smelting companies in Ile-Ife, Osun state. Concentrations of Cd, Pb, Mn and Ni in the samples were found to exceed both WHO and USEPA guideline safety limits, resulting in the deterioration status confirmed by various pollution indices. Following months of black soot enveloping the atmosphere in Port-Harcourt, the city of oil and refineries in Southern Nigeria, Kalagbor et al. (2019) determined heavy metals in the soot samples collected from residential areas. Concentrations of all the metals were higher than those in unpolluted control samples, while also exceeding WHO standard limits. In particular, Cd and Pb levels were significantly high and cancer risk assessments suggested that children in the city were at risk of developing various types of cancers (Kalagbor et al., 2019).
There have also been reports of heavy metals presence in the atmosphere in Northern Nigeria. Mafuyai et al. (2014) determined heavy metals (Pb, Cr, Fe, Mn, Cd, Zn, Cu and Ni) in respirable dusts from seven locations within Jos metropolis, Plateau state, over a period of 3 months. Concentrations of Cd, Ni and Mn were found to greatly exceed the WHO recommended limits for the metals in respirable dusts. The study attributed the presence of the metals in the samples to vehicular traffic and wastes incineration in the city (Mafuyai et al., 2014). Ayua et al. (2020) also investigated heavy metals in respirable dust and PM around industrial sites in Kano, Kaduna and Jos. Concentrations of Cd, Ni and Pb were found to be above the WHO set standard limits in some of the areas studied. The study reported strong correlation between PM and the heavy metals, thereby confirming that the contaminants indeed originated from the industrial activities. This finding also gives credence to the use of sampled air-suspended PM for the evaluation of heavy metal levels in air, as reported by most of the studies.
3.2.3 Heavy metals in ground waters, surface waters and aquatic biota species
The review revealed that water is one of the most studied environmental phases, with respect to investigations of heavy metals contamination in Nigeria. Numerous studies have considered this phase from various perspectives and motivated by different reasons. For instance, only about 10% of Nigerians have access to centrally managed clean pipe-borne water; the majority of Nigerian homes depend on underground waters, accessed via hand-dug wells and mechanically drilled borehole facilities (Idowu et al., 2022). Many rural populations also depend on water abstracted from unprotected surface sources such as streams and rivers. This situation, coupled with poor enforcement of environmental laws, which potentially exposes these water resources to contamination by various industrial and municipal wastes, has formed part of the motivation for many studies investigating levels of heavy metals in water samples. Additionally, unprotected and unmanaged streams and rivers often serve as means of recreation (i.e. swimming) to people in rural Nigeria, with the potential hazard of ingesting waters contaminated with toxic metals.
Denkok et al. (2021) determined heavy metals in various water samples, including ground water and factory-packaged satchet water, in Jos, Plateau state. The authors found that the levels of Pb, Cd, Cr, and Cu were higher than their respective WHO allowable limits in drinking water. Adeyemi and Ojekunle investigated heavy metals concentrations in underground waters (which provide drinking water to people) around industrial estates in Ogun state. High concentrations of Pb, Fe, Ni and Cr were measured in the samples, with the total hazard index (HI) showing high risk across different age groups, and particularly for infants. On the other hand, Enuneku et al. (2018) worked on water samples from boreholes sited close to some dumpsites in Benin city, Nigeria. Based on the metals pollution indices and the estimated daily dosage through drinking, it was established that the levels of metals in the boreholes posed no threat to the health of the people.
Afolayan (2018) reported heavy pollution of surface waters in Ibadan with Pb, Cd and Fe, due to the presence of a battery waste dumpsite from which these metals leach to the surface water. Odebunmi et al. (2014) worked on various ground and surface water samples from different locations in Osun state, and found that the toxic metals (Pb, Hg, As and Cd) were all higher than WHO permissible limit for drinking water. Because many Nigerian homes harvest rainwater for drinking during the rainy season, Olabanji and Adeniyi (2005) investigated heavy metals content of rain water, comparing levels in free-fall rain water to those harvested via roof tops. The study found that the metals concentrations were higher in roof-harvested rain water, with the metals content reflecting the metallic composition of the roofing material. However, levels in both water types were within safe limits and were lower than those determined for the neighbouring surface waters, packaged table waters, and vegetation-intercepted rainwater.
Ekere et al. (2014) determined levels of As, Cd, Hg, Pb, Cr, Fe and Cu in water samples from streams, lakes/ponds and hand-dug wells in rural parts of South-Eastern Nigeria. the result showed that except for Hg, other showed above the permissible limit of drinking water. The total hazard index of the metals, assessed through human oral water consumption, indicated that the water sources were mostly of high risk. As an example of studies that sought to determine seasonal variation of heavy metals in environmental matrices, Achi et al. (2021) investigated levels of Fe, Mn, Zn, Cu, Cd, Cr, Pb and Ni in water samples from Ogbere river, in Ibadan Southwestern Nigeria. Significant variation was observed for Mn, Fe, Pb, Cr, and Cd, with concentrations higher in the dry season samples than in the wet season samples.
Closely related to studies on surface waters are those examining concentrations of heavy metals in fish and other aquatic fauna. Such studies are important because they reveal the level of exposure of the organisms to toxic trace metals, which may also be passed on to humans through the food chain. Indeed, Nigerians in rural areas freely obtain food resources from many rivers and streams. Also, the use of contaminated waters for fish cultivation may result in the presence of heavy metals in fish species sold and consumed locally. Abalaka et al. (2020) determined concentrations of heavy metals in samples of Clarias gariepinus (common catfish) and Synodontis clarias (mandi) obtained at Kado fish market Abuja (North central) Nigeria. Concentrations of Cr, Fe, Cd and Cu exceeded their permissible limits, while evidence of bioaccumulation in liver was obtained for Zn, Cr, Fe and Cu. Obasohan and Eguavoen (2008) studied heavy metal levels in Erpetoichthys calabaricus (freshwater reed fish) in Ogba river, Benin city. The authors determined and compared dry and rainy season concentrations of Cu, Mn, Zn, Cr, Ni and Pb in the fish. Concentrations of the metals in the fish were all higher than in the river water, pointing to a bioaccumulation effect of metals in this fish species. The study also reported that both dry and rainy season levels of Cu, Mn and Ni exceeded their WHO permissible limits for the metals in food. Similar studies were conducted by Wegwu and Akaninwor (2006), Oguguah and Ikegwu (2017) and Olayinka-Olagunju et al. (2021) on fish resources in new Calabar river, Lagos lagoon and Ogbese river (Ondo state), respectively. Wegwu and Akaninwor (2006) further demonstrated that heavy metals presence, even at concentrations below those determined in the Nigerian rivers, caused death of fishes and inhibited hatching of their eggs. A number of studies (for example Aiyesanmi et al., 2010; Anani and Olomukoro, 2017; Aduwo and Adeniyi, 2018; Ogundele et al., 2019; and Aigberua et al., 2020) have also reported levels of heavy metals in river sediments, the bottom layer comprising soil, dead and decayed plant and animal materials, onto which metals are significantly adsorbed and may be resuspended into the water column.
3.2.4 Heavy metals in foods and beverages
Plants growing on contaminated soils may bioaccumulate heavy metals from the soil and translocate it from the root to other parts of the plant. This principle is employed in phytoremediation of lands contaminated with heavy metals. In Nigeria, edible crop plants are sometimes grown on river floodplains, which receive deposits of wastes and contaminants (including heavy metals) during flooding events (Maduawuchi et al., 2019). Metals from the soil may then transfer to vegetables and food crops growing on the floodplains. Additionally, edible crops and vegetables are found growing around waste dumpsites and factories, with the tendency of toxic metals being transferred from the soil into various plant parts. Apart from these routes, there are other potential routes through which food items may be contaminated by trace metals, and a number of studies have focussed on this subject. Akaninwor et al. (2006) compared trace metals concentrations in Nigerian staple food crops (both raw and cooked) from farmlands in Rivers state, an oil-producing area of Nigeria, to those from farmlands in non-oil producing (Ebonyi) state. Metals concentrations were found to be significantly higher in the food crops from the oil-rich region than in the same crops from the non-oil state. This result was attributed to the nature of the soil in the oil-producing area, being high in organic matter content that could chelate metals in the soil and facilitate their transfer into the crop plants. Similar report of comparatively high heavy metals content in crops from oil-producing area was made by Wegwu and Omeodu (2010).
Olutona and Daniel (2020) worked on melon seeds obtained from Northern and Southwestern part of Nigeria. Heavy metals determined in the samples were of the order: Pb > Zn > Ni > Co > Cd, with all values higher in seeds from the North than in the Southwest. Concentrations of Pb, Cd and Ni were found to be above the WHO permissible limits in samples where they were detected. Samuel and Babatunde (2021) performed health risk assessment, following the determination of heavy metals in food crops grown around an abandoned lead-zinc mining site in Tse-Faga, Benue state. High hazard quotient of 1714 and 1.143 were determined for Pb in Zea mays and Manihot esculenta, respectively. The study indeed indicated that the consumption of food crops growing in the vicinity of the abandoned mining site may cause lead poisoning in humans. Taiwo et al. (2021) investigated heavy metals in sixty samples of snacks and ‘fast-foods’ in Ijebu-ode, Southwestern Nigeria. The authors found that Fe was most abundant in the samples at concentrations up to 71.25 mg/kg (in cashew nuts). Cancer risk for Co in all the food samples exceeded the acceptable limit of 0.0001, suggesting possible development of cancer by individuals who consume the foods on regular basis. Gaya and Ikechukwu (2016) investigated levels of ten heavy metals in different types of plant-derived spices (seeds, leaves, bulbs, fruit pods and rhizomes), obtained from a market in Kano, Northern Nigeria. The spices all had excessive amounts of Co and Cu, with maximum levels in ginger (11.1 mg/kg) and African nutmeg (15.3 mg/kg), respectively. Estimated daily intake of the metals in onion, ginger, alligator pepper, utazi, Ashanti leaves, garlic, castor seeds and shallot were all above the tolerable limits set by FAO/WHO.
Apart from plant-based foods, other types of food materials produced in the country have also been investigated. For instance, environmental contamination with toxic metals affects fodder plants, pastures and drinking water sources used for livestock production. In particular, nomadic cattle roaming and rearing in Nigeria depend on waters from unprotected rivers and streams as sources of drinking water for cattle, with the animals directly ingesting water contaminated with toxic metals and other chemical substances. Heavy metal levels in tissues of food animals may therefore provide indication of the degree of meat toxicological safety, and the extent of environmental contamination by the metals. Njoga et al. (2021) determined levels of As, Cd and Pb in 450 edible samples of meat, comprising goat’s kidney, liver and muscle, obtained from regular slaughter houses in Enugu state. The study detected at least one toxic metal in 56% of the samples, with the highest mean concentrations of 0.57, 0.82 and 0.06 mg/kg recorded for As, Pb and Cd, respectively. Estimated daily intake for all the metals exceeded recommended safety limits. Because goat meat is commonly consumed in delicacies in Eastern part of Nigeria, this study highlighted the significant public health risks that the consumption of goat meats poses to humans in the region. Wegwu and Wigwe (2006) worked on edible meat/flesh of the African giant snail (Archachatina marginata), sourced from three geopolitical zones of Nigeria - Southeast, Southwest and South-south. The study quantified Cu, Fe, Zn, Ni, Pb and Cd in the snail samples and reported that the heavy metals concentrations were above the WHO limits, particularly in samples gotten from highly industrialised environments.
Benthic invertebrates such as periwinkle (Tympanotonus fuscatus), mudskipper (Periophthalmus barbarous) and Sesarmid crab (Guinearma alberti) constitute an important food (soup) ingredient in Southern parts of the country. Odigie and Olumokuro (2021) determined heavy metals content of these benthic fauna species, collected monthly from a wetland area in Delta State, over a period of 18 months. Apart from assessing the toxicological safety of their consumption, the species are bioindicators that could reveal levels of bioavailable toxic metals or other pollutants present in the rivers and sediments. Notable maximum mean concentrations of the metals measured in the species were 349.8, 3.46, 2.09, 0.41 and 0.19 mg/kg for Fe, Cu, Cd, Pb and Cr, respectively. Such levels of the metals are a cause for concern, given the widespread consumption of the invertebrate species in special delicacies in the area. Study by Azi et al. (2018) provide evidence that heavy metals are leached from raw foods into the cooking water, which is often consumed together with meals in soup preparations.
Few studies have investigated levels of toxic metals in beverages. Iwegbue (2010) analysed various brands of canned beers in Nigeria and reported that Pb, Cd, Cr, Ni and Fe were above permissible maximum levels for the metals in drinking water, while Co, Al, Cu and Zn were within the limits. Iwegbue et al. (2014) investigated heavy metals concentrations in locally produced alcoholic beverages, including raphia palm wine, oil palm wine, ogogoro, pito and burukutu, mostly consumed in rural communities in Southern Nigeria. In contrast to the result obtained for canned alcoholic (beer) drinks, the concentrations of all the metals were below permissible limits. The high concentrations of toxic trace metals in canned beers may be due to the industrial nature of the production process, which typically involves the intermediate liquors and finished products coming in contact with metallic equipment and machineries, unlike the production of traditional alcoholic drinks which employs local wooden utensils. The packaging and storage of beers in metallic cans may also be contributing to the impartation of trace metals onto the drinks. Olutona and Livingstone (2018) investigated heavy metals concentration of non-alcoholic (malt) drinks obtained from various market in Ibadan, Southwestern Nigeria. Concentration of Pb, Ni and Cr were found to be above their respective WHO limits for drinking water.
3.2.5 Heavy metals in medicine and human fluid samples
Medicines, being substances ingested to cure or lessen the effects of diseases and ailments, are normally manufactured under hygienic conditions. They are also expected to be of high purity standards, with the absence or non-detectable levels of extraneous chemical substances. In Nigeria, as it is in many developing African nations, people use orthodox/modern medicines as well as local medicines, produced from herbs and made in form of tablets or mixed bottle concoctions. Aigberua and Izah (2019) investigated levels of heavy metals in some liquid herbal medicines sold in Portharcout, Southern Nigeria. Ni, Zn, Co and Fe were determined in the concoctions at maximum concentrations of 0.068, 0.024, 0.177 and 27.1 mg/L, respectively (Fe was found in 100% of the samples). The study noted that some of the herbal medicines were not approved by the government agency regulating the production and sales of foods and drugs in Nigeria. This points to the inadequacy of surveillance and inadequacy of enforcement of relevant laws by the concerned national agencies. Similarly, Nduka et al. (2020) determined carcinogenic heavy metals (Cd, Hg, As, Cr, Pb and Ni) in 30 brands of locally manufactured painkiller medicines, randomly sourced from pharmaceutical stores in Anambra state. The metals were detected in various combinations in the samples, while Ni was found in all the painkiller samples. The study estimated total cancer risk (TCR) and total non-cancer risk (TNCR) for the heavy metals to range from 7.21 × 10− 13 – 1.25 × 10− 10 and 1.51 × 10− 7 – 5.56 × 10− 5 respectively, noting that the continuous consumption of these painkiller medicines puts people at the risk of heavy metal toxicity. Nnaneme et al. (2021) worked on orthodox analgesic syrups from pharmaceutical shops in Ibadan, Oyo state. The mean maximum concentrations reported by the study were 4.12, 3.5, 0.49, 0.67, 0.7 and 0.91 mg/L for Ni, Cd, Cr, Zn, Pb and Hg, respectively. These values are highly worrisome and cast some doubts on the correctness of the analytical procedure and processing of the ensuing data. For instance, the maximum values reported for Ni and Cd in the syrups are 58 times and 1,166 times higher than the authentic WHO guideline limits for these metals (WHO, 2017). On the other hand (though very unlikely), the results may mean that the pharmaceutical syrups indeed contain such high levels of toxic trace metals, raising even more concerns for the health and safety of the Nigerian unsuspecting public.
The presence of heavy metals in medicines and in other samples such as cosmetics, foods and water (as discussed in sections 3.2.1, 3.2.4 and 3.2.3, respectively) provide good premise and justification for studies, which investigated toxic trace metals in human samples. Adekola et al. (2001) investigated heavy metals (Cd, Pb, Zn and Cu) in scalp hair samples of 900 individuals aged between 1 and 40 years, living in Ibadan or Ilorin, Nigeria. Varying concentrations of the metals were detected in the hair samples. However, a most profound outcome of the study is the generally higher concentrations of Pb and Cd, found in hair samples of older people (16–40 years) than in hair samples of younger ones, irrespective of the location. This result provides strong indication of bioaccumulation of heavy metals in human systems, through ingestion and other means. The fact that the hair samples were thoroughly and repeatedly washed with solvents and water prior digestion (Adekola et al., 2021) exclude the possibility that the heavy metals were merely adsorbed on the surface of the hair samples. Accumulation of toxic trace metals in human body systems in Nigeria was also corroborated by findings of Akan et al. (2014), who determined Ni, Cd, Pb and As in blood and urine of patients at the University of Maiduguri Teaching Hospital (UMTH), Borno state. The authors found that the concentrations of metals increased with the age of people, being lowest in the 1–10 years group and highest in the 51–60 years age group. Furthermore, levels of the metals in blood and urine were above those in drinking water sources in Maiduguri metropolis, where the patients reside (Akan et al., 2014). Verla et al. (2019) also investigated levels of heavy metals in urine and blood samples of 60 children in Owerri metropolis, Eastern Nigeria. The study found Pb, Cd, Ni, Mn and Cr in both the urine and blood samples, with concentrations in blood being higher than those of urine samples. Indeed, the authors noted that the maximum concentrations of the metals in blood were higher than the maximum values specified by the USA Academy of paediatrics (Verla et al., 2019). Eneh (2021b) investigated toxic heavy metals concentrations in blood and urine samples of a cohort of 100 hairdressers in Enugu, believed to have been exposed to the metals through regular use of hairdressing cosmetics. Exposure to Pb was implied from a high mean blood Pb concentration of 17.47 µg/dL. The study also reported mean blood Hg level of 25.06 ng/mL, which was above the expected normal range of 10–20 ng/mL. Mean concentration of Ni (0.49 µg/dL), was found to be above the reliable value of 0.2 µg/dL. These Ni levels were noted to be possibly responsible for carcinogenic effects, that impaired the quality of life of the subjects, as indicated by the rate of dizziness, nausea, vomiting, sleeplessness and headaches (Eneh, 2021b).
3.2.6 Heavy metals in soils
Soil could be imparted with trace metals through weathering and mineralization of parent rock materials, as well as anthropogenic influences such as industrialisation, mining, indiscriminate waste dumping and automobile emissions. Particular areas of soil prone to receiving high concentrations of heavy metals in Nigeria are the waste dumpsites, serving as receptacle for all forms of solid and liquid wastes and are mostly unregulated by authorities. Aiyesanmi and Idowu (2012) reported high concentrations of heavy metals in soils of three dumpsites in Akure, Southwestern Nigeria. Order of concentration of the metals was the same in the three dumpsite soils and followed the pattern: Cu > Ni > Pb > Zn > Cr > Cd > Co. High concentrations of all the metals were also detected in edible leafy vegetables (Amaranthus spinosus and Talinum triangulae) found growing around the waste dumpsites. Eze et al. (2020) investigated heavy metals levels in four major dumpsites in South-eastern Nigeria and performed an assessment of human health risks associated with metals at the dumpsites. The study revealed that children were at the highest risk of exposure to As, Pb and Ni, with the ingestion exposure pathway being the major contributor to both the cancer and non-cancer risks. Electronic wastes, particularly the cathode and anode of batteries used in many portable devices, contain substantial amount of heavy metals and rare earth elements after their useful life (Odegbemi et al, 2021). Study by Ofudje et al. (2014) and Ibe et al. (2018) on electronics workshops and electronic wastes dumpsites in Nigeria have demonstrated the release of heavy metals from these materials. Investigation of heavy metals in soil near a battery wastes dumpsite in Ibadan, Oyo state by Afolayan (2018) revealed soil contamination factor above 6.0 for Cd, Pb and Fe, indicating excessive and severe pollution of the soil with the metals. Furthermore, the toxic metals, Cd and Pb, were found at concentrations above 2.80 and 40.0 mg/kg, respectively, in maize plants grown near the battery dumpsite. Accumulation of metals in vegetables growing around dumpsites is a major cause for concern, as unsuspecting individuals may fetch them for consumption or for sales in open markets.
Soils in the proximity of industrial sites have also attracted some attention. Two recent studies (Olatunde et al., 2020; Laniyan and Adewumi, 2020) investigated heavy metals levels of soils around different cement factories in Southwestern Nigeria. Heavy metals concentrations were higher in the soil samples, compared to the appropriate reference samples analysed in the studies. Considerable pollution and potential ecological risk from Cd, Cr, Ni and Pb were observed by Olatunde et al. (2020) for soil samples around Ibese cement factory. In addition to the proximal soil pollution with heavy metals at the Ewekoro factory, Laniyan and Adewumi (2020) detected Cu, Pb, Cr, Co and Ni in vegetables and root crops, at concentrations above international maximum safe limits. Ogundele et al. (2021) worked on soil samples from both active and abandoned artisanal gold mining sites in Ile-Ife, Nigeria. While various metals were detected in the samples, concentration of Pb was particularly high and an assessment of contamination status via geoaccumulation indices revealed that the soils were indeed contaminated with Pb.
Floodplain soils (adjacent to rivers) are commonly used in Nigeria for cultivation of food crops and vegetables, due to their alluvial nature and the availability of water for irrigation purposes. A number of recent studies have been focussing on the metals content of floodplain soils, which potentially derive from materials deposited by overflowing rivers, themselves contaminated with toxic trace metals. Maduawuchi et al. (2019) investigated levels of Pb, Co and Cr in three floodplains in Southwestern Nigeria. The study found that fluvial deposition contributed more significantly to Pb and Co contents of the floodplains, with percentage contribution ranging from 79.3–99% and 67.2–85.7%, respectively. These two metals were also detected in an edible vegetable (Amaranthus hydridus) harvested from the floodplains. Another study by Aiyesanmi et al. (2020) determined the speciation of metals in the floodplain of Onukun river, Ondo state. Cu was found to be associated with the soil organic fraction; Pb and Zn exists in reducible fractions, while Cr and Fe are associated with the residual fraction. The findings suggest that Cu, Pb and Zn were mostly contributed by fluvial deposition to the floodplains, whereas Cr and Fe determined in the soils were more of geogenic or lithologic origin. Association of Pb with reducible soil fraction and attribution to anthropogenic activities was also reported by Ebong et al. (2019). In relation to agriculture, soil of vegetable farms irrigated with wastewater have showed higher levels of heavy metals, than similar soils with no wastewater applied (Abdu et al., 2011).
3.2.7 Heavy metals in crude oil and oil-contaminated sites
Hydrocarbons and various heavy metals are common components of crude oil, bitumen, oil-bearing rocks and other valuable earth resources. A number of studies have determined heavy metals in crude-oil in Nigeria, to provide indication of the suitability of crude for refining, in terms of the tendency to cause corrosion or poison catalysts used in refinery operations (Onojake et al., 2016; Adebiyi and Adebiyi, 2015). The heavy metals present in Nigerian crude oil are mainly Cu, Mn, Fe, Zn, Pb, Co, Ni, Cd and Cr (Chinedu and Chukwuemeka, 2018). Of greater relevance to this review, however, are studies which examined heavy metals in oil sands and oil - spillage sites. An estimated 3.1 million barrels of crude oil is believed to have spilled in the Niger-Delta, the oil - endowed region of Nigeria, from 1976 to 2014 (Chinedu and Chukwuemeka, 2018). Osuji and Onajake (2004) worked on soil samples from oil-polluted lands in Obiobi and Obrikom, Niger-Delta. The study confirmed higher levels of Pb, Ni and Cu in all surface soils (0–15 cm) from oil-contaminated lands, compared to nearby ones which did not receive oil spills. Similarly, Nwaichi et al. (2016) determined heavy metals in farm soils and crops grown on 4-year-old crude-oil impacted lands in Uduvwoku and Ekore, Delta state, compared to non-oil-impacted lands in the same area. The study found much higher levels of Cd and Cr in oil-impacted farmlands than in the controls. Also, edible cassava tubers grown on the contaminated lands contained Cd and Cr at average concentrations of 0.24 and 1.33 mg/kg, respectively, exceeding WHO set limits for these metals in food, whereas the same metals were not detected in cassava from non-oil-impacted farmlands. This study exemplifies the exposure of humans in Nigeria to heavy metals, through consumption of food crops cultivated on contaminated soil environments. Similar results of elevated metals content in crops from oil - prospecting areas of Rivers state were earlier reported by Hart et al. (2005). Adebiyi and Ore (2020) determined heavy metals in sand residues (tailings) of the Nigerian bituminous sand field. Various heavy metals, including Cu, Fe, Sc, Nb, As, V, Mn, Ti, Sr and Ni were detected at high concentrations, ranging from 81.75 µg/g (As) to 9453 µg/g (Fe). Indeed, assessment of contamination revealed very high ecological risks by the level of metals present in the tailings.