Environ Monit Assess (2022) 194: 38 https://doi.org/10.1007/s10661-021-09686-8 Urbanizing with or without nature: pollution effects of human activities on water quality of major rivers that drain the Kumasi Metropolis of Ghana Godfred Darko  · Seth Obiri‑Yeboah · Stephen Appiah Takyi · Owusu Amponsah · Lawrence Sheringham Borquaye · Lydia Otoo Amponsah · Benedicta Y. Fosu‑Mensah  Received: 6 February 2021 / Accepted: 6 December 2021 / Published online: 21 December 2021 © The Author(s), under exclusive licence to Springer Nature Switzerland AG 2021 Abstract The effects of urbanization such as pop- kg for organochlorines, 0.010 mg/kg for organophos- ulation upsurge, increased industrialization, urban phates, and 0.010  mg/kg for synthetic pyrethroids), agriculture, and rural–urban migration of persons the study showed that the sediments are polluted with exert pressure on the limited water resources in petrogenic and pyrogenic polycyclic aromatic hydro- most cities. This study investigated the impact of carbons. River Subin, the most polluted among the human activities on the water and sediment qual- three rivers, recorded benzo[e]pyrene concentrations ity of the three main rivers (Wiwi, Subin, and Sun- up to 47,169 µg/kg. The geoaccumulation index and tre) in Kumasi, the second-largest city in Ghana. The concentration factors show that the rivers are highly physicochemical parameters and the concentrations contaminated with metals such as cadmium, chro- of contaminants, including heavy metals, polycyclic mium, mercury, and arsenic and are related to human aromatic hydrocarbons, pesticide residues, and micro- activities. The microbial quality of the rivers was bial loads in the rivers, were linked to the specific poor, recording specific microbial loads of 6.8, 4.1, human activities at the riverbanks. While all the 37 and 1.5 × 1 07 counts/100  mL respectively for Wiwi, pesticide residues investigated in river sediments had Subin, and the Suntre Rivers. The three water bodies concentrations below the detection limits (0.005 mg/ are therefore not suitable for recreational and irriga- tional purposes. Supplementary information The online version contains supplementary material available at https:// doi. Keywords Water pollution · Contamination · org/ 10. 1007/ s10661-0 21-0 9686-8. Industrialization · Urbanization · Environmental impact · Rural–urban migration G. Darko (*) · S. Obiri-Yeboah · L. S. Borquaye · L. O. Amponsah  Department of Chemistry, Kwame Nkrumah University of Science and Technology, Kumasi, Ghana Introduction e-mail: gdarko.sci@knust.edu.gh Water is a basic need for all life forms on the earth S. A. Takyi · O. Amponsah  Department of Planning, Kwame Nkrumah University and is an essential component in human activities in of Science and Technology, Kumasi, Ghana agricultural, domestic, industrial, and recreational set- tings. Without access to fresh water, all the sustain- B. Y. Fosu-Mensah  able development goals planned for poverty reduction Institute for Environment and Sanitation Studies, College of Basic and Applied Science, University of Ghana, and securing the general well-being of populations Legon, Accra, Ghana (UNEP, 2020) would not be attained. However, in Vol.: (0123456789) 1 3 8 Page 2 of 18 Environ Monit Assess (2022) 194: 38 developing countries, not much consideration has hydrocarbons concentrations, microbial loads, and been given to adequately secure this priceless natural pesticide residues found in the water and sediments of resource (Mishra et  al., 2019). Surface water bodies the Wiwi, Subin, and Suntre Rivers were correlated are sometimes used as receptacles for waste dump- to the human activities that take place at their banks. ing in many cities in developing countries (Boadi & This study will help improve knowledge on the rela- Kuitunen, 2002; Mbugua, 2017). Consequently, some tionships between human activities at the banks of the surface water resources have been rendered unsuit- rivers and the pollution they produce. able for human consumption due to the accumulation of large volumes of dirt, debris, and toxicants such as Relevance of the study heavy metals, pesticide residues, and polycyclic aro- matic hydrocarbons that emanate from human activi- The attainment of the Sustainable Development ties (Edokpayi et al., 2017). As the population in cit- Goals (SDGs), particularly SDG 6, 11, and 14 in ies increases, the problem of urban water pollution many cities in the global south, has been undermined will increase as more people compete for the limited by rapid and unguarded urbanization. Water bodies freshwater resources. The rate of population growth are adversely affected by rapid urbanization in cities. and urbanization are alarmingly high in some cities. In this regard, the attainment of the loveable and sus- Africa has the highest global growth rate of 3.5% tainable cities, as envisioned in the SDGs, is depend- (Saghir & Santoro, 2018). The annual population ent on our ability to manage human activities and growth rate in Ghana’s capital city, Accra, is 4.3% preserve surface water bodies properly. This study (Rain et al., 2011), while that of Kumasi (the second- is relevant to Ghana’s natural resource management largest city) is 5.6%, which is more than twice the and environmentally sustainable solutions targeting average national growth of 2.5% (Amoateng et  al., the county’s developing agenda of promoting a green 2018). The rapid population growth in the Kumasi economy. The study will also serve as a template to Metropolis has drastically increased the demands on other cities in the global south that have characteris- land for development, putting intense pressure on tics similar to Kumasi, Ghana, and reinforce the need the ever-limiting land resources around water bod- for environmental improvement in the region. ies leading to contaminations of the main water bod- ies. The riparian areas of the rivers have been under extreme human activities in recent years, adversely Methods affecting the quality and quantity of water that drain the city (Boadi et al., 2018; Keraita et al., 2003). Study area Studies have been conducted on heavy metal pollu- tion in some water bodies (Akoto et al., 2020; Opoku The Kumasi Metropolis — located approximately et al., 2020), street dusts (Rweyemamu et al., 2020), 250  km NW of Accra, the capital of Ghana — is and polycyclic aromatic hydrocarbons in soils and found between latitude 6°35′–6°40′ North and lon- water in the industrial hub of Suamein the Kumasi gitude 1°30′–1°35′ West. The Metropolis has an Metropolis (Bandowe & Nkansah, 2016). Also, approximate land area of 214.3 km2 which is occu- Monney (2013) found a drastic deterioration in the pied by some 1,730,249 inhabitants, representing water quality as River Aboabo flows through the 36.2% of the total population of the Ashanti Region densely populated areas of Aboabo, Moshie Zongo, (GSS, 2010). The population density in the Metropo- and Anloga in the Metropolis. However, none of lis is 8075 people per square kilometre. The three riv- these studies assessed the relationship between land ers studied are the main water bodies that drain the use and the type of pollutants they emit into the water Metropolis. Water and sediment samples were taken bodies. from locations (Fig. 1) along the rivers banks where Therefore, the goal of this study was to assess the human activities are pronounced from May to August impact of human activities on the quality param- 2019. Among the sampling points were light human eters of the three main rivers that drain the Kumasi activities areas (Wi1, Wi3, Wi6, Sb8, and St4), and Metropolis of Ghana. Specifically, the physicochemi- heavy human activity areas (Wi7, Wi11, St1, St2, St3, cal qualities, heavy metals and polycyclic aromatic Sb1, Sb2, Sb3, and Sb4). Vol:. (1234567890) 1 3 Environ Monit Assess (2022) 194: 38 Page 3 of 18 38 Fig. 1 Location map showing sampling points along Wiwi, Subin, and Suntre rivers that drain the urban settlement in Kumasi metropolis, Ghana Water and sediment sampling (Hageman et  al., 2019) and filled into hermetically closed borosilicate glass bottles. Physical parameters For the Wiwi, two samples were taken from upstream (pH, conductivity, temperature, total dissolved solids, points (Wi1 and Wi3), one midstream (Wi6), and two and salinity) were measured in situ using multi-meter other samples were collected downstream (Wi7 and probes (Model: Horiba U-51 and Model: HACH Wi11), spanning from Wiwiso (Wi) through Gyin- 2100 P). In the laboratory, water samples were stored yaase Junction (Wi11) where the Sisa and the Aboabo in a refrigerator at − 4  °C. Sediments were air-dried Rivers join the Wiwi River. Sampling on the Subin in a fumehood and oven-heated at 105  °C constant River covered points from its source at the Bantama weight, then pulverized and sieved through a 0.5-mm Racecourse (Sb1), through to Daaban (Sb8). Sam- metric test sieve before their storage. ples were also taken at the midsection of the river at the Abinkyi Market (Sb3). The other samples were Physicochemical parameters picked from Asokwa (Sb4) and Daaban (Sb8), where the Suntre and the Kwaada Rivers join the Subin. The turbidity of the river water samples was meas- Five other sampling points were selected from the ured using a standardized nephelometer (Hanna source at North Suntreso (St4) and two others from Instrument, Wagtech International), based on a stand- between the Bantama (St2) and North Suntreso (St1) ard method (Jain et  al., 2020). Biochemical oxygen parts of the river. The last of them (St3) was taken demand was measured as the milligrams of oxy- from the Suntre River in the North Patase section. gen consumed per day during a 5-day incubation of Surface water (0–10-cm depth) was collected water samples at 25  °C (Ma et  al., 2020). Chemical into pre-cleaned 1 L polyethene bottles. The sedi- oxygen demand was determined using the standard ment samples were collected using the grab approach dichromate titration method (Ma, 2017). Colour was Vol.: (0123456789) 1 3 3 8 Page 4 of 18 Environ Monit Assess (2022) 194: 38 determined by comparison to a reference colour disc kg for Cd, 1.29  mg/kg for Co, 4.67  mg/kg for Cr, (Magubane et al., 2019) in a Lovibond apparatus (EC 12.6 mg/kg for Cu, 0.005 mg/kg for Hg, 4.28 mg/kg 2000 Pt–Co, USA). for Ni, 7.91 mg/kg Pb, and 7.49 mg/kg for Zn from the KNUST Botanical Gardens (Akoto et  al., 2020; Trace metal analyses Opoku et al., 2020) were used. Metals in the sediments were initially screened using Pesticide residue extraction, clean up, and analysis the Niton XL3t GOLD + X-ray fluorescence spec- trometer (Rweyemamu et  al., 2020) after calibration Pesticide residue analysis was carried out by the Pes- and standardization using NIST 2709a certified refer- ticide Residues Analysis Laboratories of the Ghana ence material. The average recoveries from triplicate Standards Authority, Accra (ISO Certificate #: D-PL- runs of the reference material were satisfactory, range 15208–01-00). Reference standards for 27 pesticides from 88 ± 9% for arsenic to 99 ± 8% for zinc. The (lindane, alpha-endosulfan, beta-HCH, delta-HCH, reproducibility of the analysis was checked through aldrin, heptachlor, gamma-chlordane, dieldrin, the analysis of five duplicate samples yields a per- endrin, beta-endosulfan, p,p´-DDT, p,p´-DDD, p,p´- centage difference of ≤ 6%, indicating a satisfactory DDE, endosulfan sulphate, methoxychlor, metha- agreement of readings. Other quality checks included midophos, phorate, fonofos, diazinon, dimethoate, analysis of procedure, reagents, and control blanks, pirimiphos-methyl, chlorpyrifos, malathion, fenitrothion, as well as triplicate analysis of samples. One-quarter parathion, chlorfenvinphos, profenofos, allethrin, (25%) of all the samples, representing various set- bifenthrin, fenpropathrin, lambda-cyhalothrin, perme- tings, were analysed using a calibrated Agilent 7800 thrin, cyfluthrin, cypermethrin, fenvalerate, deltame- inductively coupled plasma-mass spectrometer (ICP- thrin) were obtained from Ehrenstorfer GmbH (Augs- MS) as a confirmatory test for the XRF analyses. For burg, Germany). this, about 1  g aliquots of sediment and water sam- About 10 g of the prepared sediment samples were ples were digested in aqua regia (1HCl:3HNO) at extracted into 10 mL aliquots of acetonitrile through 150  °C for an hour on a heating block. These were ultra-sonication for about 2  min, followed by shak- further analysed with the ICP-MS using the US-EPA ing for 30 min at 300 motions/min and then a 30-min Method 6020B (Darko et  al., 2017). The percentage standing to allow phase separation. The supernatants recoveries (92–80%) and the reproducibility (8–16%) obtained were dried using 2 g anhydrous magnesium obtained from a triplicate analysis of NIST 2710 cer- sulphate and concentrated to about 1 mL on a rotary tified reference material were satisfactory. evaporator operating at 38  °C. The extracts were cleaned up using 10  mL polypropylene cartridges Metal pollution analysis packed with activated silica gel (heated at 130 °C for 10  h). A 10-mL portion of acetonitrile was used to The occurrence and the anthropogenic contributions elute the column, and the eluate concentrated to near to the elevated concentrations of the metals defined dryness using the rotary evaporator. The residue was by the geo-accumulation and concentration factor re-dissolved in 1 mL ethyl acetate for gas chromatog- were defined by Eqs. (1) and (2): raphy (Ahammed Shabeer et al., 2018).Organochlorine and synthetic pyrethroids residual Geoaccumulation index, Igeo = log [(C ∕1.5C )] pesticide were determined using a Varian CP-3800 2 s r (1) gas chromatograph (Varian Inc. USA) coupled with Concentration factor CF = ∕ (2) CombiPAL autosampler and Ni-63 electron capture , C Cs r detector. Separation of analytes was achieved on a where Cs is the level of heavy metal measured in the capillary column (Merk, 29,806-U, SLB®-35  ms sediment and Cr is the geochemical background con- Capillary GC Column L × I.D. 30  m × 0.25  mm, df centration serving as a reference indicator. The fac- 0.50 μm) + (30 m + 10 m EZ guard column × 0.25 mm tor, 1.5, is matrix correction used to minimize the internal diameter, 0.25 µm film thickness of VF-5 ms) possible effects of variations in the environment. at injector and detector temperatures of 270  °C and Background values of 0.3  mg/kg for As, 0.01  mg/ 300  °C, respectively. The oven temperature was Vol:. (1234567890) 1 3 Environ Monit Assess (2022) 194: 38 Page 5 of 18 38 programmed at 70 °C for 2 min, ramped at 25 °C/min with 10 mL of HPLC grade acetonitrile in a 50-mL to 180 °C, and finally ramped at 5 °C/min to 300 °C centrifuge tube for a minute, followed by an Agi- giving a total runtime of 31.4  min. The carrier gas lent Bond Elut QuEChERS AOAC extraction salt was nitrogen, flowing at 1  mL/min, and the detec- packet containing 6 g of anhydrous M gSO4 and 1.5 g tor makeup gas at 29 mL/min. Aliquots (1 μL) of the of anhydrous NaOAc. The sample tubes were re- purified pesticide extract was injected by the split- vortexed for 1 min and then centrifuged at 4000 rpm less mode into the gas chromatograph (Fosu-Mensah for 5 min (Morin-Crini et al., 2020). et al., 2016). Organophosphorus residues were analysed on the Solid-phase extraction clean up same GC but using a pulse flame photometric detec- tor. The conditions for the GC analyses were capillary About a 6.0-mL portion of the upper acetonitrile column coated with VF-1701  ms (30  m × 0.25  mm layer was aliquoted into a 15-mL Bond Elut QuECh- internal diameter, 0.25 μm film thickness). The injec- ERS AOAC Dispersive SPE tube, which contained tor and detector temperature were set at 270 °C and 400 mg of primary, secondary amine exchange mate- 280  °C, respectively. The oven temperature was rial, 40 mg of C-18 EC, and 1200 mg of anhydrous programmed as follows: 70  °C for 2  min, ramp at MgSO4. The tube was vortexed for 1  min and then 25  °C  min−1 to 200  °C, held for 1  min, and finally centrifuged at 4000  rpm for 5  min. A 4-mL aliquot ramped at 20 °C  min−1 to 250 °C and maintained for of the extract was filtered through a 0.45-μm polyvi- 3.3  min. Nitrogen was used as carrier gas at a flow nylidene fluoride syringe filter; then, 100 μL of the rate of 2.0  mL  min−1 and detector makeup gases extract was injected into the HPLC system (Ankar- (17.0, 14.0, and 10.0  mL  m in−1) for air-1 hydrogen Brewoo et  al., 2020). A Cecil-Adept binary pump and air-2, respectively. The injection volume was HPLC coupled with Shimadzu 10AxL fluorescence 2.0 μL. The total run time for a sample was 14 min detector (Ex: 254  nm, Em: 390) with Phenom- (Fosu-Mensah et al., 2016; García Ríos et al., 2020). enex hyperclone BDS C18 column (150 × 4.60  mm, The concentrations of the pesticide residues identi- 5  µm). The mobile phase composition was Solution fied using the retention times of the external standard A (acetonitrile) and Solution B (deionized water) were found using peak area integration on prepared at 0.8  mL/min. Gradient elution was used with the calibration curves. The limits of detection and quan- following combination, 0–5  min: 60% A, 40% B; tification were found based on 3 and 10 times the 5–15 min: 90% A, 10% B; 20 min: 100% A, 0% B; noise/signal ratios of serially diluted samples forti- and 28–30 min: 60% A, 40% B. Polycyclic aromatic fied with certified reference material (ERM-BC403). hydrocarbons in samples were identified using the The method’s detection limit was 0.005  mg/kg for retentions times of the standards and quantified using organochlorines, 0.010 mg/kg for organophosphates, a prepared calibration curve. Analyses of samples and 0.010 mg/kg for synthetic pyrethroids. Recovery were carried out in triplicates. The limit of detec- of the internal standards ranged between 70 and 120% tion for all polycyclic aromatic hydrocarbons ranged for all pesticides analysed. from 0.10 to 6.46  ppb. Diagnostic ratios (Deelaman et al., 2020; Gao et al., 2019) were applied to predict Analysis of polycyclic aromatic hydrocarbons the characteristics and the sources of polychlorinated hydrocarbon pollution in water and sediments. A standard mix of polycyclic aromatic hydrocarbons containing 100  µg/mL each of anthracene, benzo[a] Bacteriological analysis anthracene, benzo[b]fluoranthene, benzo[k]fluoran- thene, fluoranthene, and pyrene; 200 µg/mL each of Isolation and counting of total coliforms, faecal coli- benzo [g,h,i] perylene; and fluorene and 1000 µg/mL forms, Escherichia coli, and enterococci were car- each of 1-methylnaphthalene, 2-methylnaphthalene, ried out using the most probable number method, naphthalene, and acenaphthene was obtained from using 100 mL aliquots of the water samples (Akrong Sigma Aldrich, Japan. Calibration standards ranging et al., 2019; Januário et al., 2019). Protocols for con- from 5 to 125  ng/g was prepared from the standard tamination control were strictly followed to assure mix. About 1  g aliquots of sediments were mixed data quality. Washing and cleaning procedures were Vol.: (0123456789) 1 3 3 8 Page 6 of 18 Environ Monit Assess (2022) 194: 38 thoroughly carried out, and all the glassware was correlation option was chosen for this test (Amponsah autoclaved at 121 °C at 15 pounds per pressure inch et al., 2020). for 15 min. Replicates were run to ensure the integrity of the results. Blank samples were also run to ensure there were no inherent biases in the methods used. Results and discussions Prediction of associations between human activities Human activities and land-uses and contamination A catalogue of human activities that go on along the To find the association between the contaminants and first 100 m off the banks of the rivers, together with the specific human activities that take place at the their GPS coordinates, types of samples collected, riverbanks, a non-parametric Mann–Whitney U-test and sensory analyses of the view on sites, are all (Marozzi, 2013) was used to compare differences in recorded in Table  S1 (Supplementary data). Dump- concentrations of analytes. Differences were consid- ing of household trash into the river bodies was a ered significant at p < 0.05. All data management, key human activity observed. Uncontrolled open visualization, and statistical analyses were performed burning of waste and trash dumping into the ripar- on R version 3.5.2. Principal components analysis ian areas (Fig. 2) were commonly observed along the (PCA) was conducted using the PAST (Paleonto- river banks. All three rivers were littered with single- logical Statistics Software Package for Education and use plastics. Plastic pipes were also seen connected Data Analysis) software (Paleontological Electronica, directly from some household sewage systems into Denmark) to identify associations between the dif- the rivers. Other observations include the use of the ferent datasets and to find underlying patterns. The riverbanks as farmlands, residences, creeks, vehicle Fig. 2 A picture showing some human activities observed bays sited. The riverbank of Wiwi at Wiwiso (C) shows animal at the riparian areas of the water bodies that flow through the dung by free-range animals. The Subin River (D) close to the Kumasi metropolis in Ghana. The riparian areas along the Abinkyi Market shows some indiscriminate trash disposals in Suntre River (A and B) has auto-fitting shops and car washing and along the river course Vol:. (1234567890) 1 3 Environ Monit Assess (2022) 194: 38 Page 7 of 18 38 washing bays, and auto-mechanic workshops. There Central Market, and the entire Adum and Asafo town- were also the disposal points for junk metal parts, ships. The waste generated from these places com- glasses, and plastics along the rivers. bined with siltation arising from the unpaved areas that direct their surface runoff into the river may have Water quality analyses contributed to the high turbidity in the river. The turbidity distributions of the three rivers in the light Physical and chemical properties of the rivers and heavy human activity areas differed significantly in Kumasi (Mann–Whitney U = 17.5, p < 0.05, 2-tailed). The temperature recorded across the three rivers Colour was stable due to the stable ambient air temperature (Table  1). The water temperature showed no statis- The Suntre River is colourless from its source at tically significant difference (p > 0.05) in areas of North Suntreso (St4). However, the river runs black heavy and light human activities at the riverbanks. just about 200  m away at Abrepo Junction (point The pH value recorded was within the WHO allow- located between St1 and St4) where it is joined by a able value of 6.5–8.5 (WHO, 2011) and showed no drain. The Subin River is black at the source (Sb1), statistically significant differences (p > 0.05) in heavy midstream (Sb3), and downstream (Sb4), where it and light human activity areas. flows through concrete storm channels in the central business district of the Metropolis. It, however, turns Turbidity brownish-grey at the Daaban area (Sb8), where it joins the Kwaada and Suntre Rivers. The colour of all Turbidity ranged from 0.575 to 10.30 NTU for the the water samples was outside the WHO permissible Wiwi River, 4.30 to 16.75 NTU for the Subin River, limit of 5 Hazens (WHO, 2011). Colour in surface and 2.36 to 19.50 NTU for the Suntre River (Table 1). water results from the leaching of organic materials The Subin River recorded the highest turbidity (16.75 and is, primarily, the result of dissolved and colloi- NTU). The water samples were filled with black col- dal substances present (Garbowski, 2019). Overall, loids resulting from the dissolution of organic matter the colour of the rivers indicates a health threat to (Setareh et al., 2021) released into the water from the those who use the water (Völker & Kistemann, 2011). markets sited along the river at both banks. Also, sus- However, the water colour at the light and heavy pended matter and microorganisms might cause tur- human activity areas was not significantly different bidity. The mean turbidity for the three rivers (Wiwi (p = 0.282). 7.84 NTU, Subin 10.30 NTU, and Suntre 7.26 NTU) was above the set upper allowable limit of 5 NTU Total dissolved solids, electrical conductivity, (WHO, 2011). The release of untreated waste efflu- and salinity ents into the rivers and suspended matter may have contributed to the high turbidity recorded. Except for the electrical conductivity in the Subin The Subin River receives untreated waste from River, most of the other physical parameters, includ- various places in the Metropolis, including the Keje- ing total dissolved solids and salinity (Fig.  3), were tia Mall Complex, the Kumasi Zoological Gardens, higher than the acceptable standards of the World the Komfo Anokye Teaching Hospital, the Kumasi Health Organization (WHO, 2011). The total Table 1 The mean and corresponding standard deviations of the physical properties (temperature, pH, turbidity, colour) of Wiwi, Subin, and Suntre rivers in Kumasi, Ghana Water sample Temperature (°C) pH Turbidity (NTU) Colour (Hazen) Wiwi 28.12 ± 0.08 6.65 ± 0.81 7.72 ± 4.49 34 ± 8.94 Subin 26.6 ± 0.35 6.93 ± 0.49 10.29 ± 5.84 640 ± 260.80 Suntre 26.05 ± 0.13 7.08 ± 0.25 8.79 ± 7.51 650 ± 191.50 Vol.: (0123456789) 1 3 3 8 Page 8 of 18 Environ Monit Assess (2022) 194: 38 1200 B 1000 C Wiwi Subin Suntre 800 B C B 600 B A C 400 A A 200 B CA C A 0 Conductivity (μS/cm) TDS (mg/L) Salinity (mg/L) Total Hardness Total Alkalinity (mg/L) (mg/L) Fig. 3 The mean and standard deviation of the physical properties of the three main rivers; Wiwi (A), Subin (B), and Suntre (C), in Kumasi, Ghana, showing high levels of conductivity, dissolved solids, and colour dissolved solids found in the Subin River exceeded could be a result of the dilution effect of the Daaban the recommended level of 500 mg/L for aquatic life to River. thrive (US EPA, 1988). Generally, all the rivers had high salinity and total dissolved solids, which showed Nutrients: nitrates and phosphates no statistically significant differences (p > 0.05) in heavy and light human activity areas. The satellite The three rivers recorded nitrate concentrations markets and refuse dumps sited at the banks of the above the WHO limit of 5.0  mg/L (WHO, 2017). rivers could be the cause of the high conductivity The high nitrate concentrations indicate the three and total dissolved solids (Akanchise et al., 2020) in rivers are highly polluted (Fig.  4). The mean phos- the Subin and Suntre Rivers. Conductivity was high- phate concentrations were 0.67 ± 0.33, 0.45 ± 0.11, est in the Subin River. However, electrical conduc- and 0.47 ± 0.27 mg/L for Wiwi, Subin, and the Sun- tivity showed no statistically significant differences tre Rivers, respectively (Fig. 4). The phosphate con- (p > 0.05) across the three rivers in heavy and light centrations were relatively high compared to the human activity areas. natural background of 0.02  mg/L (WHO, 2017). Except for three points on the Suntre River, all other sites recorded values higher than the WHO limit of Total alkalinity and hardness not greater than 0.3  mg/L (WHO, 2017). The high concentrations of phosphates may be due to seep- In the Wiwi River, total alkalinity and hardness val- ages from decomposed organic trash from dumpsites ues ranged from 40 to 80 mg/L and 25 to 250 mg/L, (Onyekwelu & Aghamelu, 2019), domestic wastewa- respectively (Fig. 4). Total alkalinity and hardness at ter and agricultural runoffs deposited into the water the Subin River were 40–180 mg/L and 25–100 mg/L, bodies (Saadat et  al., 2018), and the application respectively. In the Subin River, alkalinity and water of phosphorus-containing agrochemicals by veg- hardness were comparatively low where the Daaban etable farmers along the Wiwi River from Wiwiso River and Subin River meet (Sample point Sb8). This (Wi1) through to Gyinyaase (Wi11). High phosphate Vol:. (1234567890) 1 3 Levels of Physico-Chemical properties Environ Monit Assess (2022) 194: 38 Page 9 of 18 38 Fig. 4 Mean levels and standard deviations of the chemical properties of the Wiwi, Subin, and Wiwi Rivers found in the Kumasi Metropolis concentration is responsible for the eutrophication of water bodies are polluted based on their biochemical a water body as phosphorus is a limiting nutrient for and chemical oxygen demands. This could be due to algae growth (WHO, 2017). It would then lead to the the rivers’ proximity to dumpsites, which could con- proliferation of phytoplankton and their decompo- tribute to the loading of organic matter into the water sition over time, leading to a high chemical oxygen bodies. The implication of high biochemical oxygen demand. demand in the rivers is that the oxygen present in the water will be used to decompose materials, and thus, Biochemical and chemical oxygen demands is unavailable for aquatic life. The principal component analysis for phys- Oxygen demands for chemical or biochemical pro- icochemical parameters is given in Fig.  5. All the cesses are indicators of the quantities of decom- three rivers have a similar description of their phys- posing organic matter present in the water body icochemical parameters by the first and second axes (Findlay, 2021). The mean biological oxygen demand (Fig.  5a), which together explain 66% (Fig.  5b) of in the Wiwi, Subin, and Suntre rivers was 7.84 ± 1.64, the total variation in the datasets. According to the 8.00 ± 1.90, and 9.50 ± 2.39  mg/L, respectively. The loadings plot (Fig.  5c), conductivity, TDS, salinity, mean chemical oxygen demand for the Wiwi, Subin, and colour trend positively together in the first com- and Suntre Rivers were 35 ± 4.72, 28.9 ± 6.79, and ponent, meaning that these parameters have a simi- 34.32 ± 4.08  mg/L, respectively. But the acceptable lar occurrence in the rivers. To the first component, limits are 2 mg/L and 20 mg/L, respectively (WHO, Subin and Suntre contribute the most. To the second 2011). The natural background levels of biochemi- component, Wiwi and Subin contribute the most, and cal oxygen demand for freshwater range from 1.0 to the third component, Wiwi and Suntre contribute to 3.0 mg/L (WHO, 2017). This implies that all the most to the formation of that axis. For all the three Vol.: (0123456789) 1 3 3 8 Page 10 of 18 Environ Monit Assess (2022) 194: 38 Fig. 5 Scree plot, scores, and loadings of principal component analyses of physicochemical parameters in rivers Wiwi, Subin, and Suntre in the Kumasi metropolis components, conductivity, TDS, and salinity trend for organochlorines, < 0.010  mg/kg for organophos- together with the same strength. Similarly, the turbid- phates, and < 0.010 mg/kg for synthetic pyrethroids). ity and total alkalinity trend together with the same strength. In the first component, temperature trends Polycyclic aromatic hydrocarbons negatively with all other parameters, meaning that as temperature increases in the river, the other param- Eighteen polycyclic aromatic hydrocarbons (PAH) eters decrease. were investigated in the sediments of Wiwi, Subin, and the Suntre rivers (Fig.  6). The mean levels of Sediment quality analysis the polycyclic aromatic hydrocarbons in the Wiwi, Subin, and Suntre Rivers in Kumasi ranged from Pesticide residues non-detections (acenaphthalene in all three rivers) to 9482.89 μg/kg (Benzo[e]pyrene) in Subin. Naph- None of the water bodies showed detectable levels of thalene and its derivatives (acenaphthene, acenaph- the 37 pesticide residues (including 13 organophos- thylene, and fluorene) were the predominant PAH phorus pesticides, 15 organochlorines, and 9 synthetic in the sediments. The mean concentrations of naph- pyrethroids) investigated in the sediments. However, thalene (172.22  μg/kg), acenaphthene (12.53  μg/ that is not a confirmation of the absence of any pes- kg), acenaphthylene (67.53  μg/kg), and fluorene ticides as the residues may just be below the detec- (18.43  μg/kg) in the sediments of all three rivers tion limits of the equipment used (< 0.005  mg/kg exceeded the recommended exposure limits. At these Vol:. (1234567890) 1 3 Environ Monit Assess (2022) 194: 38 Page 11 of 18 38 Fig. 6 Concentrations of the polycyclic aromatic hydrocarbons found in the sediments of Rivers Wiwi, Subin, and Suntre in the Kumasi metropolis in Ghana concentrations, benthic organisms could suffer in Probable carcinogenic and mutagenic toxicities health leading to their deaths (McGrath et al., 2019). of polycyclic aromatic hydrocarbons in the rivers Though residents in Kumasi do not directly consume in Kumasi these waters, they are used for domestic chores in the surrounding communities such as Asago, just Seven carcinogenic PAH including benzo[a]anthra- 9  km from the central business district (Kumasi cene, chrysene, benzo[b]fluoranthene, benzo[k] et al., 2011). Children swim in the rivers while oth- fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, ers fish in the Wiwi River (Wi6 and Wi7) and in the and indeno[1,2,3-c,d]pyrene accounted for a major Daaban sections (Sb8) where the Subin, Suntre, and portion of all the 18 PAH measured in the sediments the Kwaada Rivers join. The Wiwi River serves as (Fig. 6). The highest level of carcinogenic PAH in the irrigation water for vegetable farmers along the river sediments was recorded in Subin and Suntre. This sug- from the upstream (Wi1 and Wi3) through to the gests industrial effluents are discharged into the rivers. downstream (Wi6, Wi7, and Wi11). The people who Also, leachates from various approved and illegal (con- consume food products from this polluted water body venient) dumpsites found around may contribute sig- are very likely to be exposed to the contaminants. nificantly to the pollution of the rivers. Vol.: (0123456789) 1 3 3 8 Page 12 of 18 Environ Monit Assess (2022) 194: 38 The diagnostic ratios show that the rivers are by air from distant sources and later became mobile polluted by PAH compounds of both petrogenic in runoffs (Gaurav et al., 2021). and pyrogenic sources. A point on the Wiwi River recorded 100% petrogenic contaminations, whereas Pollution indices of the rivers’ sediments two points on River Subin recorded 100% pyrogenic PAH contamination. Results from the Wiwi River The heavy metal concentrations in the sediments of showed that only two points (Wi3 and Wi11) where the three rivers (Wiwi, Subin, and Suntre) are pre- there are heavy vehicular activities) had petrogenic sented in Fig. 7. PAH pollution. The possible human activities that Except for mercury, the highest concentrations may have contributed to the pollution are outlined of all the metals were found in the Suntre River. All (Supplementary Table  S1). However, the frequen- the points on Subin and Wiwi rivers recorded chro- cies of the sources of PAH pollutants found were mium concentrations higher than 100  mg/L. All the not consistent with the specific human activities rivers recorded chromium and cobalt concentrations carried along the rivers, thus, ruling them out as greater than 50  mg/L at all points. Sediments from the point sources for the pollutions. Therefore, the the Wiwi River consistently measured more than pollution could result from atmospheric depositions 60  mg/kg of chromium throughout its course. For from non-point sources (Jia et al., 2019). The poly- example, a point close to the Abinkyi Market (Sb3) cyclic aromatic hydrocarbons could have travelled on the Subin River recorded lead concentrations of Fig. 7 Boxplot of heavy metals concentrations found in rivers Wiwi, Subin, and Suntre in the Kumasi metropolis of Ghana Vol:. (1234567890) 1 3 Environ Monit Assess (2022) 194: 38 Page 13 of 18 38 157.73 mg/kg. The average concentration of Pb in the Hg, and Zn) at the river’s source at the Racecourse Subin River was 46 mg/kg. River sediments could be (Sb1). The Igeo values for Subin River sediments the major sources of Pb contamination (Islam et al., indicated high to extremely high levels of contamina- 2018). It is a ubiquitous pollutant that could find its tion of heavy metals (As, Cd, Co, Cr, Hg, and Zn) at way into water bodies through the discharge of indus- the river’s source at Bantama (Sb1), Kumasi Zoologi- trial effluents (Islam et al., 2018). However, none of cal Gardens (Sb2), and Abinkyi Market (Sb3). such companies was located along the three rivers in this study. Heavy metal concentrations at sites in Concentration factors of metals in the river sediments the vicinity of heavy human activities did not differ significantly (p > 0.05) from those in the area of light Concentration factors (Table  2) were employed to human activities. determine the extent of human contributions to the contaminations of metals river sediments in Kumasi. Geoaccumulation indices of metals in the river Among the studied metals, Cu in the sediments of sediments Wiwi was not from anthropogenic sources (Varol, 2011). Pb in the Wiwi sediments was not high enough The rivers are polluted with various toxic met- to pollute the river downstream (Wi11). The Igeo als (Table  2). The Subin River was the most pol- values indicate that the present levels of Cu and Pb luted with heavy metals. Toxic metal concentrations at Subin’s source (Sb1) do not strongly contribute to exceeding the background levels indicate pollution pollution. However, just about 500 m from the source, due to human activities (Li et  al., 2020). The con- at Sb2, the sediments samples were moderately con- centrations of the heavy metals found in the river taminated with Pb. The Suntre River sediment sam- are about 10 times the background levels. The Igeo ples were polluted with Cd and Hg at all the river sec- values were 10.26 (Cd), and 9.4 (Hg) in the sediment tions (St1, St2, and St4). A similar observation about samples of the Wiwi River. The Igeo showed that all Cd and Hg was made of the sediments from the Wiwi the points on the Wiwi River were contaminated with and Subin. Human activities were found to be the Cd, Hg, Co, and Cr. The Igeo for the Subin River leading cause of pollution in all cases. sediment samples indicated high to extremely high The main human activity that could connect the contamination with heavy metals (As, Cd, Co, Cr, heavy metals polluting the rivers in Kumasi is the Table 2 The geoaccumulation and concentration factors of metals found in the Wiwi, Subin, and Suntre rivers of Kumasi, Ghana Geoaccumulation indexa Concentration factorb Wiwi Subin Suntre Wiwi Subin Suntre As 3.32 3.68 3.41 15.37 19.55 16.43 Cd 10.41 10.02 9.92 2065 1663 1471 Co 4.68 5.73 5.10 38.56 85.75 51.74 Cr 2.48 4.00 3.65 12.94 24.15 18.87 Cu 0.28 0.47 0.01 0.76 2.08 1.29 Ni 1.09 1.54 1.47 3.86 4.39 4.15 Pb 0.00 1.08 1.09 0.67 5.82 4.15 Hg 9.38 9.61 9.52 1004 1181 1100 Zn 1.66 2.94 2.70 4.80 13.54 9.88 a For the geoaccumulation indices, the results of metal contamination were categorized into six purity classes as Igeo < 0, class 0 (uncontaminated sediments); 0 < Igeo < 1: class I (uncontaminated to moderately contaminated sediments); 1 < Igeo < 2: class II (moderately contaminated sediments); 2 < Igeo < 3:class III (moderately to highly contaminated sediments); 3 < Igeo < 4: class IV (highly contaminated sediments); 4 < Igeo < 5: class V (highly to extremely contaminated sediments); Igeo > 5: class VI (extremely contaminated sediments) as presented in Table 4.13 (Duncan et al., 2018; El-Sayed et al., 2015) b The contamination categorizations were in an increasing order rated from 1 to 6, with 0 = none, 1 = none to medium, 2 = moderate, 3 = moderate to strong, 4 = strongly polluted, 5 = strong to very strong, 6 = very strong (Varol, 2011) Vol.: (0123456789) 1 3 3 8 Page 14 of 18 Environ Monit Assess (2022) 194: 38 practice of urban agriculture (Kubier et  al., 2020). contrast, Suntre is slightly more aligned to the first This study could not link phosphate fertilizer usage component, indicating that this river is the most pol- to the farming activities that go on along the Wiwi luted. The loadings in the first two components are River. Moreover, the Subin and the Suntre had no shown in the loadings plot (Fig. 8b). The variables agricultural activities, yet the same metals polluted with the greatest influence in the loadings for PC1 them. Elevated concentrations of other trace met- are Co, Cr, Cu, Hg, Ni, Pb, and Zn. These variables als, such as Pb, which can also occur as impurities are directed almost entirely along PC1, indicating in phosphate fertilizers, were identified as pollutants a common occurrence of these metals at the same from human activities. place at the same time. The PC2 is influenced more strongly by As and Cd. All the metals, except cad- Principal component analysis of metals in the river mium and antimony, tend to occur at high concen- sediments trations at the same time in the rivers, as evidenced by high loadings to the first axis. This could be as The results of the principal component analysis of a result of the human activities carried out in and the heavy metals are given in Fig. 8. The scores plot around the rivers. The scree plot (Fig.  8c) shows (Fig.  8a) shows the scores for the first two com- that the first and second components are the most ponents. Rivers Subin and Wiwi had most of their important for this analysis because they have eigen- variance explained by the second component. In values ≥ 1. The first component (or axis) explains Fig. 8 Scree plot, scores, and loadings of principal component analysis of heavy metals in rivers Wiwi, Subin, and Suntre Vol:. (1234567890) 1 3 Environ Monit Assess (2022) 194: 38 Page 15 of 18 38 71% of the total variation within the datasets, and time may have resulted in this level of pollution. the second explains 11%. Domestic effluents are allowed into the river with- out going through any form of water treatment. The Microbiological qualities of water from the rivers garbage from homes dumped at the riverbanks and in Kumasi the practice of open defaecation were common phe- nomena at all sampling sites, with exceptions to St4 The results of the microbiological quality of water and Wi11. samples from the Wiwi, Subin, and the Suntre The Wiwi River is mainly used as irrigation Rivers are shown in Fig.  9. The mean of the total water for the countless stretch of vegetable farms coliforms, faecal coliforms, Escherichia coli, sited along the river from Wiwiso (Wi1) through to and faecal enterococci counts in the water sam- Gyinyaase (Wi11). Subin and Suntre also registered ples were 1.932 × 1 014, 4.1 × 1 09, 3.1 × 1 06, and very high counts of total coliforms (2.35 × 1 015 79.88 × 102  CFU/100  mL, respectively, all of counts/100 mL). The water bodies are influenced by which surpassed the allowable limits of 400 total several human activities such as hospitals, markets, coliforms/100  mL and 10 faecal coliforms (E. and schools that discharge their wastes directly into coli)/100 mL (GEPA, 1994). The enormously high them. counts of the microbial load in the three rivers Under this investigation, the rivers in Kumasi show they are extremely polluted with faecal mat- scored zero passes in quality when the EU Guide- ter. The sources of the three rivers defy the odds line Directive of less than 100 faecal coliforms per in the microbial loads. The source of the Wiwi 100  mL and 100 enterococci per 100  mL of water River, for example, had 2.35 × 1013  CFU/100  mL was used. The same conclusion could be made for total coliforms, 4.15 × 1010  CFU/100  mL for based on the Imperative Directive of < 2000 fae- faecal coliforms, 2.35 × 1 08  CFU/100  mL E. coli, cal coliforms per 100  mL. These water bodies are and 1.2066 × 1 04  CFU/100  mL faecal enterococci. not suitable for irrigational and recreational pur- However, the counts quickly increased more than poses. The E. coli counts in sites with heavy human tenfold as the water passed through a nearby set- activities were statistically higher than sites with tlement area. The human activities recorded at the light human activities (Mann–Whitney U = 40.5, Fig. 9 Summary of the microbiological quality of water from the Wiwi, Subin, and the Suntre rivers in the Kumasi metropolis showing A faecal coliform counts and Escherichia coli counts and B faecal counts and faecal enterococci count Vol.: (0123456789) 1 3 3 8 Page 16 of 18 Environ Monit Assess (2022) 194: 38 p = 0.029). Other microbial measures showed no from abandoned dump sites in Kumasi, Ghana. Scientific significant differences between heavy and light African, 10, e00614. https:// doi. org/ 10. 1016/j.s ciaf.2 020. activities sites. e00614Akoto, O., Gyimah, E., Zhan, Z., Xu, H., & Nimako, C. (2020). Evaluation of health risks associated with trace metal exposure in water from the Barekese reservoir in Kumasi, Conclusions Ghana. Human and Ecological Risk Assessment: An Inter- national Journal, 26(4), 1134–1148. https:// doi.o rg/ 10. 1080/ 10807 039. 2018.1 55903 3 All the three rivers (Subin, Wiwi, and Suntre) in the Akrong, M. O., Amu-Mensah, F. K., Amu-Mensah, M. A., Kumasi metropolis are polluted due to human activi- Darko, H., Addico, G. N. D., & Ampofo, J. A. (2019). Sea- ties found along the banks (within the first 100  m). sonal analysis of bacteriological quality of drinking water The water bodies are highly contaminated with sources in communities surrounding Lake Bosomtwe in the Ashanti Region of Ghana. Applied Water Science, microorganisms and toxic chemical species such as 9(4), 82. https:// doi. org/ 10. 1007/ s13201- 019-0 959-z heavy metals and polycyclic aromatic hydrocarbons. Amoateng, P., Finlayson, C. M., Howard, J., & Wilson, B. Biological and chemical oxygen demands of the riv- (2018). A multi-faceted analysis of annual flood inci- ers are very high, and the waters appear coloured. dences in Kumasi, Ghana. International Journal of Disas-ter Risk Reduction, 27, 105–117. https:// doi. org/ 10.1 016/j. Pollution of the rivers is highest upstream and may ijdrr.2 017. 09. 044 affect lives in the watercourse. The physicochemical Amponsah, L. O., Dodd, M., & Darko, G. (2020). Gastric bio- characteristics of the rivers do not render them con- accessibility and human health risks associated with soil ducive for irrigation in urban agriculture or recrea- metal exposure via ingestion at an E-waste recycling site in Kumasi, Ghana. Environmental Geochemistry and Health, tional activities. It is recommended that the surface 1–13. https:// doi.o rg/ 10. 1007/s 10653- 020- 00760-7 waters in Kumasi be adequately managed by restrict- Ankar-Brewoo, G. M., Darko, G., Abaidoo, R. C., Dalsgaard, ing the land use at riverbanks and maintaining buffer A., Johnson, P., Ellis, W. O., & Brimer, L. (2020).  Die- areas as pressure points during flooding. The water tary risk assessment due to the consumption of polycy-clic aromatic hydrocarbon in two commonly consumed from these rivers should not be used for irrigational street vended foods. Polycyclic Aromatic Compounds, or recreational purposes. 1–11. https:// doi. org/ 10. 1080/ 10406 638.2 020. 18301 28 Bandowe, B. A. M., & Nkansah, M. A. (2016). Occurrence, Acknowledgements We are also grateful to the SHEATHE distribution and health risk from polycyclic aromatic com- Project (www. sheat he. org) hosted by the Department of chem- pounds (PAHs, oxygenated-PAHs and azaarenes) in street istry, KNUST, Kumasi, Ghana, for using their laboratory dust from a major West African Metropolis. Science of resources. the Total Environment, 553, 439–449. https:// doi. org/ 10. 1016/j. scito tenv. 2016.0 2. 142 Boadi, K. O., & Kuitunen, M. (2002). Urban waste pollution in Funding This study was financially supported by the Kwame the Korle Lagoon, Accra, Ghana. The Environmentalist, Nkrumah University of Science and Technology Research 22(4), 301–309. https://d oi.o rg/ 10. 1023/A:1 02070 67285 69 Fund (KReF). Boadi, N. O., Borquaye, L. S., Darko, G., Wemegah, D. D., Declarations Agorsor, D., & Akrofi, R. (2018). Assessment of the qual- ity of the Owabi reservoir and its tributaries. 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