Continental J. Water, Air and Soil Pollution 3 (1): 12 16, 2012 ISSN: 2251 - 0508 http://www.wiloludjournal.

.com Wilolud Journals, 2012 Printed in Nigeria doi:10.5707/cjwasp.2012.3.1.12.16

DETERMINATION OF CALCIUM, MAGNESIUM AND TOTAL HARDNESS CONCENTRATIONS IN DRINKING WATER SUPPLY IN EBONYI STATE, NIGERIA Joseph N. Afiukwa, 2Celestine A. Afiukwa and 3Wilberforce Oti Department of Industrial Chemistry, Ebonyi State University, Private Mail Bag 053 Abakaliki, Nigeria. 2 Department of Biochemistry/Biotechnology, Ebonyi State University, Private, Mail Bag 053, Abakaliki, Nigeria.
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ABSTRACT The status of public water supplies from different water sources in Ebonyi State comprising 23 underground, 7 spring and 22 surface water samples were studied. Fifty two samples were analyzed for calcium, magnesium and total hardness concentrations using EDTA titration Method. The results of three replicate determinations across nine Local Government Areas studied indicated an average total hardness of 134.13 + 15.60 mg/L CaCO3 during the rainy season (RS) and 128.8 + 16.1 mg/L CaCO3 at the dry season (DS) for groundwater, 65.55 + 2.20 mg/L CaCO3 (RS) and 65.07 + 2.21 mg/L CaCO3 (DS) for surface water and 17.2 + 2.1 mg/L CaCO3 (RS) and 17.8 + 2.0 mg/L CaCO3 (DS) for the spring water samples. The results of the analysis showed that groundwater in most parts of the State are hard compared with the WHO guideline limits, while the spring and surface waters are soft based on the WHO and U.S.-EPA guideline classifications. The results also indicated high level of calcium hardness in comparison with the magnesium hardness for both the ground and surface waters. The health and economic impacts of both hard and soft water types are discussed. KEYWORDS: Water Hardness, Health Effects, Ebonyi State, groundwater and Surface water INTRODUCTION Water is said to be hard when it does not lather readily with soap. A considerable amount of soap is required for such water to produce lather. Groundwater is generally hard compared with surface water. This however depends on the local geology and the nature of soils over which the water traverses. Therefore hardness of water may vary considerably between locations. Dissolved calcium and magnesium ions have been identified as the major contributors to hardness in natural waters (Ademoroti, 1996 and Miroslav and Vladimir, 1999). Some other polyvalent cations such as aluminium, iron, magnesium, strontium and zinc may also contribute to hardness, but their effects is very insignificant due to their low concentrations in natural waters (Ademoroti, 1996 and Miroslav and Vladimir, 1999). These ions may be present in significant concentrations especially in industrial wastewater (Ademoroti, 1996). In an environment, such as Ebonyi State, dominated by limestone (CaCO3), gypsum (CaSO4.2H2O) and dolomite (CaCO3.MgCO3), enough of these minerals ordinarily dissolve particularly in a low pH soil, to furnish Ca2+ and Mg2+ ions in water. The dissolution process is usually enhanced in aquifers with a relatively high microbial activity, which produces carbon(iv)oxide in water. The CO2 gas lowers the water pH thereby shifting the carbonate balance towards the hydrogen carbonate (Smith in Lettterman, 1999), i.e CaCO3 + H2O + CO2 Ca(HCO3)2.

This acidic condition causes a greater dissolution of calcium and magnesium salts in the aquifer rocks. Water hardness is classified into carbonate (temporary) and non-carbonate (permanent) hardness. The temporary hard water is due to the presence of hydrogen carbonate of Ca2+ or Mg2+ ions, while permanent hard water is caused mainly by the presence of chlorides and sulphates of calcium or magnesium. The total hardness of water is the sum of calcium and magnesium hardness expressed as mg/LCaCO3. Hardness in

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Joseph N. Afiukwa et al.,: Continental J. Water, Air and Soil Pollution 3 (1): 12 16, 2012

excess of the WHO permissible limits renders the water unpalatable for drinking, hinders cooking or baking and impedes laundry works as well as increases the chances of corrosion and encrustation in heated metallic pipelines or industrial boilers (Stocchi, 1990). In addition to the cost implications in laundries, very hard water is also undesirable for use in the beverage, food, batteries, paper mills, tanneries and textile industries (Gerard, 1998). Beside the beneficial effects of hard water such as the development of a healthy teeth and bones, neutralization of acid deposition and reduction in the solubility of toxic metals, the status of water whether hard or soft has also been associated with some health-related problems. The purpose of this study therefore, is to evaluate the levels of hardness in public water supplies in Ebonyi State. The results would serve as a baseline data for water quality, which may be required for domestic, agricultural, recreational and industrial uses. MATERIALS AND METHODS Fifty-two (52) water samples were randomly collected from nine, out of the thirteen Local Government Areas of Ebonyi State in February through December, 2007 and assessed for calcium, magnesium and total hardness concentrations. The samples were collected in two seasons, dry season (February, October and December, 2007) and rainy season (June, July and September) of the same year. The samples were stored separately in plastic bottles previously washed with conc.HNO3 and later rinsed with the sampled water during sampling. The calcium and total hardness were determined by standard methods using ethylene diaminetetraacetic acid (EDTA) complexometric titration (Ademoroti, 1996; Mendham et-al, 2000 and Ming, 2001), while the magnesium hardness was calculated by the difference between the total and calcium hardness. Descriptive statistics was used to analyse the data RESULTS AND DISCUSSION The concentrations of calcium, magnesium and total hardness in different water supply sources across the State were studied at two seasons and the results are presented in Table 1. The results were compared with the WHO and U.S-EPA guideline limits. The WHO classified water that contains < 50 100 mg/LCaCO3 as soft and > 100 mg/LCaCO3 as hard, while US-EPA classified water with 0 60 mg/L CaCO3 as soft and > 60 mg/LCaCO3 as hard. The results of this study indicated an average total hardness of borehole (B/h) and well waters as 134.13 + 15.64 mg/LCaCO3 at the rainy season and 128.78 + 16.10 mg/LCaCO3 during the dry season. This represents an excess of 25.4 % and 22.3 % at both seasons respectively when compared with the WHO minimum reference values for total hardness. The surface water samples showed a mean total hardness of 68.5 + 7.7 mg/LCaCO3 at the rainy season and 67.95 + 7.8 mg/LCaCO3 during the dry season indicating that the water is moderately soft by the same standards.
Table 1: Mean Seasonal Variations of the Levels of Hardness (mg/LCaCO3) in water supplies in Ebonyi State Parameters Ca-hardness Mg-hardness Total hardness Mean + SE GW Range 90.30 + 11.59 91.80 + 12.64 r 8.0 200.00 d 10.0 210.00
d r d r

36.4 + 5.07 35.9 + 7.50 0.0 80.0 0.0 80.0 22.72+ 2.71 22.52 + 2.72 4.00 64.0 4.00 64.0 5.84 + 0.7 5.21 + 0.6 3.00 8.4 3.00 7.0

134.13 + 15.64 128.78 + 16.10 10.0 312.00 11.0 290.00 68.50 + 7.70 67.95 + 7.80 12.0 166.0 13.0 166.0 17.16 + 2.11 17.80 + 1.96 8.0 26.00 8.0 23.00

Mean + SE SW Range

45.75 + 5.49 41.41 + 5.59 r 8.0 102.00 d 8.0 102.00

r d

Mean + SE SPW Range

11.71 + 1.0 11.96 + 1.8 r 9.0 18.0 d 5.0 19.0

GW= groundwater, SW= surface water, SPW= spring water, SE= standard error, r = rainy season d = dry season.

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Joseph N. Afiukwa et al.,: Continental J. Water, Air and Soil Pollution 3 (1): 12 16, 2012

The spring water samples on the other hand are relatively very soft as the results showed an average total hardness of 17.16 + 2.11mg/LCaCO3 at the rainy season and 17.8 + 1.96 mg/LCaCO3 during the dry seasons. In all the samples, calcium ions contributed a higher percentage of the total hardness than magnesium ions as the results indicated. The concentration of calcium hardness more than doubled the values obtained for the magnesium hardness. This is in line with similar studies conducted in the area (Afiukwa, 2010). A post-hoc comparison of the results between the seasons reveals that there were no significant seasonal variations in hardness concentrations for both classes of water. However, significant variations existed between the levels of hardness in groundwater compared with the surface water samples. It is observed from Fig.1, that except the spring water samples, which of course are not widely distributed across the State, the groundwater samples obtained from boreholes and public wells indicated a higher degree of hardness than surface water samples.
160

Water hardness (mg/L)

140 120 100 80 60 40 20 0

Ca Hardness Mg Hardness Total hardness

RS DS RS DS RS DS RS DS RS DS RS DS RS DS RS DS RS DS RS DS WHO B/h Well Spring Mean River Stream Dam Pond Tap Rain

Water sources Fig.1: Mean concentrations of total, calcium and magnesium hardness in ground and surface water supply sources in Ebonyi State during the rainy and dry seasons

The observed dip in Fig.1 indicates hardness levels of spring and rain waters. Although spring water is an aspect of underground water, those assessed within the study areas (Afikpo North and South) were found to be very soft contrary to expectations. This is attested to by the low pH range observed for the spring water samples (4.2 5.6). It may also mean that the concentrations of limestone, dolomite and other hardness causing mineral salts in the type of rock that dominated the area are very low. The observed results are perhaps indicative of the local geology of the study areas. The grade of limestone deposit in the area is high. This among other factors such as the topography of the land forms and nearness to railway line may have influenced the citing of the defunct Eastern Nigercem in the 1960s, a cement producing factory at Nkalagu near Abakaliki Metropolis. More of such deposits of limestone have been identified in several locations within Ebonyi State (Oyibe, 2000). Current research efforts have determined the quality and quantity to be high enough to commence the State owned cement factories at the three senatorial zones of the State. In addition to this wide spread of limestone deposits, the high solvent power of water, its slow flow-rate and the longer residence time within the aquifers, contamination of groundwater by calcium ions are expected compared with the effects of human activities such as quarries on surface waters. Fig. 2 shows the mean distributions of calcium, magnesium and total hardness concentrations in groundwater across the Local Government Areas studied at the two seasons. There were significant variations of this parameter in groundwater within the study areas. The total hardness across the L.G.As decreased in the order: Izzi (Iz) > Ezza North (Ez) > Ebonyi (Eb) > Abakaliki (Ai) > Ikwo (Ik) among the areas with high hard water in excess of the guideline limits.

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Joseph N. Afiukwa et al.,: Continental J. Water, Air and Soil Pollution 3 (1): 12 16, 2012

20 18 16 14 12 10 8 6 40 20 0 WH

Water hardness (mg/L)

Ca Hardness RS Ca Hardness DS Mg Hardness RS Mg Hardness DS Total hardness RS Total hardness DS

Ik

Afs

Afn

Sample Areas Fig.2: Concentrations of total, calcium and magnesium hardness in groundwater supply in different L.G.As of Ebonyi State during the rainy and dry seasons.

The WHO recommended 100 mg/LCaCO3 as the minimum guideline limit for total hardness in drinking water. Water supply meant for public consumption which hardness is in excess of this value is undesirable (Stocchi, 1990) and may constitute a health risk especially for the teaming population within the study areas who may depend on such water for their regular needs. Health Experts have shown that hard water taken for a long period especially that containing magnesium sulphate prolongs the duration of thrombin induced shape changes in bovine platelets and can also weaken the stomach permanently (Austin, 1984). On the other hand, soft water is usually acidic and has been linked with incidences of cardiovascular diseases as well as acidosis (Miroslav and Vladimir, 1999, Ming, 2001). Consumers of such water may be predisposed to high dosage of chemical toxins because of acid enhanced metal dissolution. According to Medical Experts, even mild acidosis may lead to cardiovascular damage, constriction of the blood vessels and reduction in oxygen level (Ogundipe and Obinna, 2008). Other side effects in agricultural, industrial and other civil uses have been reviewed (Stocchi, 1990 and Gerard, 1998). On civil uses, it hinders cooking, baking and impedes washing with soap due to the precipitation of soap as scum. On industrial level, the furring of kettles and clogging on electrical appliances or pipelines causes encrustation, lowers the efficiency of heat exchange and causes local supper-heating and explosion (Austin, 1984). In food processing and beverage industries, paper mills, tanneries, dyestuff and electrical units such as batteries cannot be fed with very hard water (Gerard, 1998). In textiles and laundries, hard water wastes soap and detergents. Hard water however is important in the development of a healthy teeth and strong bones. Its scale formation on pipelines prevents possible dissolution of toxic metals such as lead and arsenic and reduces the solubility of these metals. CONCLUSION The study has shown that virtually all groundwater supplies in Ebonyi State are moderately hard. The high level of calcium mineral salts in the State indicated in this study is yet to be fully exploited. Finally, the study provides a baseline data on water hardness in the State. ACKNOWLEDGEMENT The authors acknowledge with thanks the Department of Industrial Chemistry Laboratory, Ebonyi State University for the provision of reagents and materials used in the analysis. REFERENCES Ademoroti, C.M.A (1996). Standard Methods for Water and Effluent Analysis, pp.40 43

Foludex Press Ltd; Ibadan

Afiukwa, J. N. (2010). Comparative Studies on Hardness Concentrations in groundwater supply from Abakaliki, Ikwo and Ishielu L.G.As in Ebonyi State, Nigeria. J. Poll. Res. 29(4): 727-731.

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Joseph N. Afiukwa et al.,: Continental J. Water, Air and Soil Pollution 3 (1): 12 16, 2012

Austin, G. T (1984). Shreves Chemical Process Industries. McGraw-Hill Book Company, New York p. 19 Encyclopedia of Chemical Technology 2nd Ed. Vol.21 p.693 Gerard, K. (1998). Environmental Engineering; Irwin / McGraw- Hill Book Company, Singapore pp.1, 456 Mendham, J; Denney, R.C; Barnes, J.D and Thomas, M.J.K (2000). Vogels Quantitative Chemical analysis 6th ed; Pearson Educational Ltd. Singapore pp. 385 -386 Ming HO.YU (2001). Environmental Toxicology: Impacts of Environmental Toxicants on Living Systems. Lewis Publishers, London pp.151 179 Miroslav, R and Vladimir, N. B (1999). Practical Environmental Analysis, Royal Society of Chemistry, U.K p.178 Ogundipe, S and Obinna, C. (2008). Safety of Table Water goes beyond the Bottle In: Good Health Weekly, Vanguard Newspapers, Tuesday, May 20, 2008 p.42 Oyibe, S. (2000). Investment Potentials, Tourism and Natural Resources Base for Raw Materials in Ebonyi State. Ministry of Commerce, Industry and Technology Publications, Abakaliki pp. 21-23. Smith, S.A In: Letterman, D.R (1999). Water Quality and Treatment: A Handbook of Community Water Supplies 5th ed. American Water Works Association. McGraw-Hill Inc. New York p.21 Stocchi, E. (1990). Industrial Chemistry Vol.1 Ellis Horwood, New York pp.131-132 Received for Publication: 04/02/2012 Accepted for Publication: 21/03/2012 Corresponding Author Joseph N. Afiukwa, Department of Industrial Chemistry, Ebonyi State University, Private Mail Bag 053 Abakaliki, Nigeria. Email: josephafiukwa@yahoo.com

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