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ESTATE FARMS IN WESTERN KENYA
BY OMWOMA SOLOMON
A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Chemistry
Department of Chemistry
Student: This thesis is my original work and has not been previously presented for a degree in Maseno University or in any other University. The work herein has all sources of information supported by relevant references. Omwoma Solomon, Sign: ____________date _________. Supervisors: This thesis has been submitted for examination with our approval as the University supervisors.
Prof. Joseph O. Lalah, Department of Chemical Sciences and Technology, The Kenya Polytechnic University College, Sign: ___________date_________.
Dr. David M.K. Ongeri, Department of Chemistry, Maseno University. Sign: ___________date_________.
In addition. ii . help. I can never forget Department of Chemistry technical bench led by the late Mr. special thanks go to Mr. Mr. Ogur is recognized for his fatherly advice. Nyahanga. Okoth for my computer proficiency skills. support and close supervision throughout my study. Dr. I pay respect to Prof.O.K. Mr. Ligawa. Lalah and Dr. Were are highly honored for the specialized training in research. All the department lecturers including Dr. Owuor and Prof.M. Manguro for their help when my career seemed to come to a standstill. Mrs. Ojwach are appreciated for my training during course work. Not forgetting my friends Mr. Jondiko.Acknowledgement Great tribute goes to Prof. Kowenje and Dr. Ochieng and Mr. Okeyo with whom we worked together in the laboratories. love and care. Amoke for their technical guidance during the entire study. Special thanks go to Prof. Finally my wife. is venerated for her patience. Okal. Ongeri for their timely advice. Mr. D. Derese and Dr. Barasa and Mr. Beatrice Omwoma. Bowa for their unquantified help. Prof. Dr. J.
iii .Dedication To my two siblings Jackson Vikwese and Mitchel Kavulani.
Heavy metals and physicochemical parameters cause a great threat to the environment and human health if the levels go beyond allowable limits. In addition the surface runoffs and soil erosions were also transporting the nitrate and phosphate residues from the fertilizers applied to the aquatic environment leading to pollution of the water.05) (two factor experiment) and students t-test (P ≤ 0. Nzoia sugarcane nucleus farms were used to represent sugarcane farming in the whole sugar belt region where Nzoia River transverses. The nitrogenous fertilizers used in the farms were also found to contain residues of heavy metals. The Presence of heavy metals in the aquatic environment also affects some physicochemical parameter like dissolved oxygen and chemical oxygen demand which become harmful to the aquatic animals and plants when they exceed certain limits. total phosphates and total organic carbon respectively. nitrate-nitrogen and dissolved oxygen beyond international levels. A pH meter. Triplicates of surface water. a mercury thermometer. bioavailability and mobility of heavy metals. there was need to determine point sources of the above parameters in order to suggest possible mitigation procedures. In addition. Sampling was done twice in the year (dry season when there was no nitrogenous fertilizer application and wet season a week after nitrogenous fertilizer application). dissolved oxygen. iv . turbidity and electrical conductivity respectively insitu. Presence of heavy metals into the aquatic environment increased water conductivity levels and reduced dissolved oxygen in water due to bioavailability and reoxidation processes respectively. were used in determining nitrate-nitrogen.05) used to check the variations. Nzoia Sugar Company in western Kenya uses nitrogenous fertilizers in sugarcane farming and the effect of these agrochemicals on the environment were yet to be determined. these fertilizers also contain residues of heavy metals that accumulate in soils and water bodies over time. chemical oxygen demand. The data was analyzed using Analysis of variance (ANOVA) (p ≤ 0. The research found out that lowering of soil pH by nitrogenous fertilizers affected the concentrations of heavy metals in the soils and the surrounding aquatic environments. Anils’ method and Okalebos’ method. a turbidity meter and an electrical conductivity meter were used to measure pH. Therefore. temperature. canals and River Kuywa (a river that traverses the nucleus to join River Nzoia) were collected. closed reflux colometric method. River Nzoia is already reported to be affected by heavy metals and physicochemical parameters like total phosphate.Abstract Continued use of nitrogenous fertilizers and biosolids in farming is known to affect the soil pH of the farms leading to acidic environment that promotes solubility. Ultraviolet spectrophotometric screening method. whereas AAS (AA-6200. Two factor completely randomized block design was used in sampling. Surface runoffs and soil erosions in the sugar plantations were the major transport agents of the heavy metals in soils to aquatic environments as was determined from high water turbidity values during the long wet season. Wrinklers’ method. surface sediments and top soil samples from the farms. Shimadzu) was used to analyze heavy metals.
Discussion...................3...............................4.......................55 4......................4.......1............2.......................... Heavy metals in Sediments 4.......................... Recommendations 67 67 67 68 68 5......47 4.........................18 4......Table of contents Abstract iv 2.................... Discussion................................................................ Heavy metals in water 4.......1 Discussion...................2...........................................5.................................................................... Conclusions 5...... Iron..............5.2.................................................2...........................2................1..................................................2................................... References 68 69 Abbreviations / Acronyms AM AAS AEC AR Arithmetic Mean Atomic Absorption Spectrophotometer Anion Exchange Capacities Analar Reagent v ......................17 2................ Recommendations for future research 5...................1............ Physicochemical parameters in water 41 49 56 4............................................................ Chromium ........13 2...............3.......................................62 Chapter 5 5.......16 2......................4....3.............................15 2........................................................1............2................................................................................................3...........39 4........................................ Zinc.................... Summary 5.................................................2.. Copper.......................... Lead..........2............. Discussion....1..................4..........1.................
CCC CEC COD Cond CMC CV DAP DDP DO DNA EC EU FAO ha hrs KEBS L LSD Ltd LD50 M mg NAS NSC OC ppm R RDA RNA SD STD Temp TCH TOC Criterion Continuous Concentrations Cation Exchange Capacities Chemical Oxygen Demand Conductivity Criteria Maximum Concentrations Coefficient of Variation Diammonium Phosphate District Development Plan for Kenya Dissolved oxygen Deoxyribonucleic Acid Electrical Conductivity European Union Food and Agriculture Organization hectare hours Kenya Bureau of Standards liter Least Significant Difference Limited Lethal Dose to kill half of population concerned molar/molarity milligrams National Academy of Sciences Nzoia Sugar Company Organic Carbon parts per million River Recommended Daily Allowable Ribonucleic Acid Standard Deviation Standard Temperature Tonnes of Cane per Hectare Total Organic Carbon vi .
Turb TP UK US USA USEPA WHO Turbidity Total Phosphates United Kingdom United States United States of America United States Environmental Protection Agency World Health Organization vii .
35 Table 4. 38 Table 4.3. 2 Table 2. 37 Table 4.1.1. Mean site variations of heavy metal loads in surface water from canals within Nzoia nucleus estate farms (in µg/L) between the long wet and dry seasons.3. Site variations of heavy metal loads in surface water from River Kuywa within Nzoia nucleus estate farms (in µg/L) between the long wet and dry seasons. Heavy metal loads in fertilizers used in the farms of Nzoia nucleus estate farms (mean ± SD mg/kg dry weight) in comparison to international standards.1.b.2.a. NA: Not Applied. 38 Table 4. 2 Source: Agronomy section Nzoia Sugar Company.List of tables Table 1. 44 Table 4. 41 Table 4.1.4. 45 viii .1. Site variations of heavy metal loads in surface water from River Kuywa within Nzoia nucleus estate farms (in µg/L) between the long wet and dry seasons. Monthly rainfall data during 1988 -1992 in Bungoma District western Kenya (Rainfall in mm). History of repeated nitrogenous fertilizer application (in bags of 50 kg each) in the studied plots from Nzoia nucleus estate sugarcane farms in Western Kenya.3. This study in comparison with international standard on heavy metals in soils (mg/kg of dry soil).18.104.22.168. Site variations of heavy metal loads in surface water from canals within Nzoia nucleus estate farms (in µg/L) between the long wet and dry seasons.1. Correlation matrix of selected physicochemical parameters and heavy metals in top soils from the nucleus of Nzoia Sugar Company and a control farm between the long wet and dry seasons. Mean site variations of selected physicochemical parameters and heavy metals in top soils from the nucleus of Nzoia Sugar Company and a control farm between the long wet and dry seasons. Estimated potential acidity produced through nitrogenous fertilizers in sugarcane plantations. 37 Table 4.2.b. Correlation matrix of heavy metal loads in water samples from canals within Nzoia Sugar Company nucleus estate farms. 35 Table 4.2. 9 Table 4.2.1. Mean site variations of heavy metals in top soils from the nucleus of Nzoia Sugar Company and a control farm between the long wet and dry seasons. Risk based analysis of DAP fertilizer used in the farms of Nzoia nucleus estate for 50 years (in Kg/Ha) in comparison to international standards. 42 Table 4.5. 2 Table 1.2. 43 Table 22.214.171.124.a.1.
126.96.36.199. 46 Table 4. Mean site variations of heavy metal loads in surface sediments from canals within Nzoia nucleus estate farms in mg/kg between the long wet and dry seasons. Correlation matrix of trace metal loads in water samples from River Kuywa.6. Correlation matrix of heavy metal loads (mg/kg of dry weight) in sediments from River Kuywa.4.4. Comparing with some studies done on sediments from other rivers53 Table 4.Table 188.8.131.52. Comparing with some international standards on domestic water and data from other studies for heavy metals.3. Mean site variation of some water quality physicochemical parameters in canals inside the nucleus estate farms of Nzoia Sugar Company between the long wet and dry seasons.b. 51 Table 4. Mean site variations of heavy metal loads in surface sediments from River Kuywa within Nzoia nucleus estate farms in mg/kg between the long wet and dry seasons.a. 60 ix .5. 58 Table 4.5. Mean site variation of some water quality physicochemical parameters from River Kuywa inside the nucleus estate farms of Nzoia Sugar Company between the long wet and dry seasons.3.3.1. 59 Table 4. Mean site variation of some water quality physicochemical parameters in canals inside the nucleus estate farms of Nzoia Sugar Company between the long wet and dry seasons.1. Correlation matrix of heavy metal loads (mg/kg of dry weight) in sediments samples from canals within Nzoia Sugar Company nucleus estate farms.2. 52 Table 4.4. 50 Table 4. Mean site variations of heavy metal loads in surface sediments from River Kuywa within Nzoia nucleus estate farms in mg/kg between the long wet and dry seasons. 51 Table 4.1.3. Correlation matrix of heavy metal loads and physicochemical parameters in water samples from canals in Nzoia nucleus estate farms.a. 50 Table 184.108.40.206. Mean site variations of heavy metal loads in surface sediments from canals within Nzoia nucleus estate farms in mg/kg between the long wet and dry seasons.3.4. 58 Table 4.4. 53 Table 4.b. 46 Table 4. 56 Table 4. 57 Table 4. Correlation matrix of physicochemical parameters of water samples from canals within Nzoia nucleus estate farms. Mean site variation of some water quality physicochemical parameters from River Kuywa inside the nucleus estate farms of Nzoia Sugar Company between the long wet and dry seasons.4.3.4.
28 x .4.4. Comparing with some international standards on domestic water and levels of metals reported in other studies for physicochemical parameters.9. A sketched map of Nzoia Sugar Company Nucleus estate farms and sampling points. 62 List of figures Figure 3. 61 Table 4.4. Correlation matrix of heavy metal loads (µg/L) and physicochemical parameters in water samples from River Kuywa.1. Correlation matrix of physicochemical parameters of water samples from River Kuywa. 61 Table 4.7.Table 4.8.
20 km from Bungoma Town and five kilometers off the Bungoma . Elgon. 2004). 2004). 1996). the pH of top soils under sugarcane cultivation decreased from 6. In Fiji.0º 36’ 14. Kakamega and Lugari Districts (Nzoia Sugar Company profile. it has been found that the change in soil pH is mainly due to the use of acidifying nitrogenous fertilizers such as Urea and ammonium phosphates. It lies between 34º 39’ 03.Webuye highway in Western province and within Kenya’s sugar belt. 1 .7 was recorded over 19 years of cane cultivation (Oliver.34º 42’ 15. 2009). 1996). 2004). 2009). River Kuywa.0 to 4. The company occupies a total surface area of 4.89”E longitudes and 0º 31’ 34.5 to 4.500 ha. a decrease of 5.24’’N latitudes.500 ha. Currently. in the nucleus with an average plant crop yield of 124 TCH (Tones of Cane per Hectare) and Ratoon crop yield of 93 TCH (Nzoia Sugar Company profile.629 ha.000 ha.000 farmers within Bungoma. 2009). the area under cane is 3. 2004). coupled with nitrate leaching that occurs under the high rainfall conditions that often prevail in cane cultivation areas (Oliver. Major cane varieties cultivated include N14.6 was recorded over the first 6 years of cane cultivation and in Philippines.2.90”E . supplies 20% of sugarcane requirement for the company and the rest is by out-grower section with a total area of 16. DDP.5 to 5.17”N . is highly depended upon by residents downstream for small scale fishing and other domestic uses (DDP. Nitrogenous fertilizers (Diammonium Phosphate (DAP) and Urea) are applied at the onset of the long rainy season that begins in March (Table 1. The Nucleus Estate. Sugarcane farming is known to reduce soil pH (Oliver. which traverses the nucleus from Mt. whose total area is 4. The factory serves over 30. In Papua New Guinea. CO421 and CO945 which are renowned for their high sucrose content (Nzoia Sugar Company profile.8 between 1979 and 1996 (Oliver.1 and 1.Chapter 1 Introduction Nzoia Sugar Company is located in Bungoma District. From existing literature. a decline in soil pH from 5.
68 (ha) DAP NA 7 5 NA NA 12 Urea NA NA 7 10 7 24 413 3.5 135.0 Urea NA NA NA NA NA 0.9 132.6 175.7 85.11 (ha) DAP NA 10 9 9 NA 38 Urea NA NA NA NA 5 5.0 124.9 99.1 191.4 105.1 72.9 65.6 152.2 207.1.1 14.7 163.7 90.1 88.8 132.9 235.7 79.9 1989 2.5 105. 1996.9 24.0 73. History of repeated nitrogenous fertilizer application (in bags of 50 kg each) in the studied plots from Nzoia nucleus estate sugarcane farms in Western Kenya.9 81. Furthermore.6 69.9 70.3 163.5 60.2. bioavailable and mobile (Alloway 1995a).1 97.5 86.21 (ha) DAP NA 20 NA NA 10 30 Urea NA NA 9 NA 7 16 616 2.7 301.5 74. Table 1.4 124.0 243 4.7 172. Hence use of nitrogenous fertilizers affects the acidity of soils thus making heavy metals readily available for transportation from soils to the aquatic environment especially during the long rainy season as compared to the long dry season due to surface runoffs.2 64. 2004).48 (ha) DAP NA NA 8 10 b NA 18 Urea NA 18 NA NA NA 18 125 3.6 101. NA: Not Applied. For instance.4 25.00 Source: Agronomy section Nzoia Sugar Company.9 Source: DDP.7 342. Month January February March April May June July August September October November December Mean Monthly Rainfall Long term mean monthly 1988 75. reduction of soil pH makes heavy metals in the soil to become more soluble.44 62.2 104.0 Urea NA NA NA NA NA 0. A Change in soil pH is usually accompanied with other chemical changes in both the soil and the receiving waters (Oliver.2 68.3 1990 58.8 68.4 107.Table 1.1 204.8 118. leaching and erosion of the soils.2 20.43 (ha) DAP NA NA NA 8 NA 8 Urea NA 10 10 NA 10 30 429 1.7 46. Plots 9053 Size Year 2005/06 2006/07 2007/08 2008/09 2009/10 Sum 20 (ha) DAP NA NA NA NA NA 0.4 47.1 67.0 8071 10 (ha) DAP NA NA NA NA NA 0.3 88.6 55.1 86.1 56.4 135. Monthly rainfall data during 1988 -1992 in Bungoma District western Kenya (Rainfall in mm).1 84.8 116.4 70.3 47.1 138.0 61.3 174.7 115.0 129.3 118.1 1991 90.7 76.5 86.6 1992 10.18 165.5 71.5 285.1 187.6 83.04 162.02 118. use of biosolids as fertilizers in 2 .3 87.
However. Driscoll et al. Lawrence and Brian (2002) also support the same arguments indicating that this has drawn the attention of farmers. and public policymakers. In addition to the above problems associated with nitrogenous fertilizers. First. This reduces metal adsorption by cation exchange and organic complexation (Ford et al. 1995b). Contaminated food webs can also couse health and economic disadvantages to people as contaminated commercial foods like fish become restricted or banned due to high metal burdens (Wang.sugarcane farming increases the total organic carbon of the soil hence influencing heavy metal transport (Xue. Second. Driscoll et al. Gough and Herring.. of important concern is the fact that use of these fertilizers affects the soil pH and from Alloway’s findings. Gough and Herring. sedimentation and precipitation (Odiete. ionization of metals increases at low pH thereby increasing their water solubility and mobility (Alloway. Ongley. consumers. It has been reported that heavy metal concentration in sediments can be several orders of magnitude greater than in water (Odiete.. chemical conditions in soil like soil pH are important secondary determinants of heavy metal transport and fate at the application sites (Alloway. 1999). 1994. 1999). 2008). and may also represent a long-term source of contamination to higher trophic organisms (Odiete . 1995b). chemical oxygen 3 . 2001). 1994. Bioaccumulation and bioconcentration of toxic heavy metal residues in aquatic environments can result in their transfer into food chains putting terrestrial consumers including humans and birds at risk (Wang. Once heavy metals find their way into the aquatic environments. Sediment associated heavy metals pose a direct risk to detrital and deposit feeding benthic organisms. hydroxonium ions (H3O+) displace most other cations on negative surface charges (Alloway. a large amount gets deposited into the sediments due to other factors like dilution factor.2).. 1987. 1995b). 1996). Mortvedt (1995) reports that nitrogenous fertilizers are contaminated with heavy metals that accumulate in soil with repeated application (Table 1. Alloway (1995a) also has reported that inorganic fertilizers contain traces of heavy metals that accumulate in soils with repeated applications. Heavy metal solubility can be affected by several factors including temperature and pH changes (Carmen et al. 1993. 1993. Ongley. 1996).1999). However. 2001). presence of the heavy metals in an aquatic environment can also affect its water electrical conductivity.. 1987. environmental organizations.
(2008). nutrients cause taste and odor problems that result in reduced recreational use. which have detrimental effects on the water quality (Fried et al. This research therefore focused on finding the concentrations of heavy metal loads and some physicochemical parameters in water. LVEMP. The heavy metal loads. 1982). In addition. Soltanpour and Raley (1989) have reported several adverse effects that may arise if the above physicochemical parameters go beyond allowable limits.340 total N tonnes per year and 946 total P tonnes per year. Most of the inorganic nitrogen and phosphates applied find their way into aquatic environments due to surface runoffs. during the rainy seasons and leaching into ground water. 1991). Problem statements According to Lalah et al. 2003. 2003). sediments and soils in the long dry season and long rainy season in Nzoia nucleus estate farms from western Kenya..1.. 2003). Onyari and 4 . Such effects include death of aquatic animals due to lack of oxygen (Richard. and increased water treatment costs (Fried et al. pH and total organic carbon from the nucleus soil farms were compared to those from an adjacent control farm where fertilizers were not being used.. 2003). 1. River Nzoia is loaded with heavy metals and the main farming activity in the Nzoia River basin is sugarcane farming.demand and dissolved oxygen (Duinker et al. Additionally. These were the values partly responsible for growth of water hyacinth in Lake Victoria hence the need to determine their point sources. Algal blooms and water hyacinth deplete the oxygen supply in the water system and are harmful to other aquatic species (LVEMP. Previous studies have shown that the addition of these nutrients to the water system would result in large proliferations of algae and water hyacinth. Cowi (2002) has indicated that annual loads of nitrogen and phosphorous in Lake Victoria from Nzoia River basin as 3. the concentrations of heavy metals in the nitrogenous fertilizers (DAP and Urea) used for sugarcane farming were also tested. another major concern in the use of nitrogenous and phosphorous fertilizers in sugarcane farming is the fact that not all the applied fertilizers are utilized in the soils. However.
infertility. This in turn affects the concentrations of nutrients in the recipient aquatic environment (Lake Victoria Environmental Management Programme (LVEMP).3. 1. (1989) also reported the same problem at the mouth of River Nzoia in Lake Victoria. birth effects. it is concluded that sugarcane farming overtime affects heavy metal concentrations and other physicochemical parameters in the aquatic environment. Ongley. Most of the research in sugar industry has been on the effects of nitrogenous fertilizers on soil pH with reference to sugarcane productivity yet the effect of the reduced pH on Heavy metal mobility and water quality parameters have not been covered extensively. 2003. the applied fertilizers will find their way into the aquatic environment through surface runoffs. These high loads of nutrients can cause changes in water quality and heavy metal distribution within the aquatic environment.2. These were the values that are partly responsible for growth of water hyacinth in Lake Victoria hence the need to determine their point sources. bioavailability and mobility of heavy metals (Alloway. NAS 1980. 2003). The presence of heavy metals in the aquatic environment also affects other physicochemical parameters in the same environment. tumor (chromium). soil erosion and leaching from their point of application. Sugarcane farming activities in Nzoia sugarcane zone that includes nitrogenous fertilizers application are believed to be the main source of these heavy metals. DO and EC which affect water quality also change due to sugarcane farming activities and need to be monitored. Heavy metals have numerous effects on human health including: Wilson's disease (copper). Other parameters such as pH. Low soil pH has been reported to affect the solubility. From the above statements therefore. Furthermore. carcinogenicity and trade regulations whereby certain foods like fish are banned in the global market due to high metal contamination levels (USEPA 1980. Snyder et al. 1. Lead arthragia (lead). Dennis et al. Cowi (2002) has indicated that pollution loading into Lake Victoria from Nzoia River basin is 3. 1975. Research justification Nitrogenous fertilizers including DAP and Urea used in sugarcane farming in the nucleus farms have been reported to lower soil pH (Oliver.340 tonnes total N per year and 946 tonnes total P per year.Wandiga. 1996). TOC. 2004). 1995a). Objectives 5 . COD.
Cu. Zn and Fe) loads between the long wet and long dry seasons in the top soils from various sites within Nzoia Sugarcane nucleus estate farms and compare them with an adjacent farm that do not use nitrogenous fertilizers 2.4. EC. canals.Main objective This study aimed at determining the levels and the variations of heavy metal loads (Pb. 1. To determine the levels and the variations in water quality physicochemical parameters namely Temp. To determine the concentrations of heavy metals in the fertilizers used (DAP and Urea) in farming activities within Nzoia nucleus estate farms. Fe) and physicochemical parameters (temperature. To determine the levels and the variations in pH. To determine the levels and the variations in heavy metal (Pb. 3. COD. Cu. and surface water in Nzoia sugarcane farms. Total Organic Carbon (TOC). Turbidity. Zn. surface sediments. DO. and Fe) loads in the surface sediments and surface water samples from canals within the nucleus estate farms and River Kuywa between the long wet and long dry seasons. 4. Chemical Oxygen Demand (COD). Dissolved Oxygen (DO). Electrical Conductivity (EC). TOC and heavy metal (Pb. Cr. Cu. Turb. NO3-N and TP in canals within the nucleus estate farms and River Kuywa between the long wet and long dry seasons. NO3-N and Total Phosphates) in top soils. TOC. and River Kuywa during the long wet (April – June) season and the long dry season (January – March). Specific objective 1. Hypotheses Null hypothesis H0: 6 . Zn. Cr. pH. pH. Cr.
and their variation between seasons and within sites were due to nitrogenous fertilizer application in the Nzoia nucleus estate farms during the long wet season.. 2. H0: µ1 = µ2 Where: H0 = the null hypothesis µ1 = the mean of population 1 (site n or long dry season) µ2 = the mean of population 2 (site n or long wet season) n: 1. Chapter 2 Literature review 7 . 3…. such that in case of any difference it was not associated with nitrogenous fertilizers applied during the wet season but other natural factors. Alternative hypothesis H1: The changes in the means of heavy metal loads and physicochemical parameters respectively.That there were no changes in the means of heavy metal loads and physicochemical parameters within sites and between the long wet and long dry seasons. 3. 2. H1: µ1 ≤ µ2 Where:H1 = the alternative hypothesis µ1 = the mean of population 1 (site1 or long dry season) µ2 = the mean of population 2 (site n or long wet season) n: 1..
1.1.2... 1995). However. continual acidification of these soils is likely to occur through the use of high inputs of ammonium-based nitrogen fertilizer inputs. environmental and edaphic factors (Wood et al. Processes of acidification The nitrification of ammonium based fertilizers such as urea and organic N in crop residues (Organic Matter) is in itself an acidifying reaction. The reaction is carried out through the microbial conversion of NH4+ to NO3 with the consequent production of protons (H+). The extent of acid generation by fertilizers is a function of the fertilizer type. Acidification of soils is usually accompanied with fertility loss and declining productivity (Ahern et al. Soil acidification Soil acidification (declining soil pH due to net proton (H+) accumulation) is a natural process that occurs during pedogenesis and is often associated with high rates of leaching. The theoretical 8 . Under intensive agricultural production. 2003).1. the rate of acidification can be accelerated through farming activities with the result that the soil resource may become significantly degraded. with Diammonium phosphate being the most acidifying and urea the least on the basis of N per kg fertilizer applied.1. 1995). 1995). 2. the high level of base removal as a result of crop uptake and subsequent removal and the generally high rainfall environment of the region which facilitates the losses of basic cations through leaching (Moody and Aitken.1. Degradation of the soil resource through the loss of fertility that accompanies acidification results in declining productivity and places the products of farming systems operating in acidifying environments subject to scrutiny under the recent ISO 14000 treaty (Moody and Aitken. Estimates of potential net acidity generated by frequently used fertilizer sources in the sugar industry are presented in Table 2. In view of the potential acidity generated by nitrogenous fertilizers the equivalent amount of CaCO3 required to neutralize this acidity is also shown in table 2.
Table 2.through the nitrification process for nitrogenous fertilizers is a net proton accumulating reaction.3 965 9 .from ammoniumbased fertilizer is a significant source of acidity generation in these production systems. The result is an accumulation of H+ at point of production and net alkalization due to the uptake of NO3. Although the production of NO3. the addition of basic nitrate fertilizers such as Ca(NO3)2 causes little change in pH due to the lack of nitrification and may in some cases result in an increase in soil pH (Woods et al.1..+ H2PO4 + H2O kmoles H+ ha-1 13.072 0. there is spatial disjunction between the production of NO3.. As long as nitrate is taken up at the point of production the outcome is neutral (Wood et al. 2003). resulting in an accumulation of protons at the point of nitrification (Haynes.amount of CaCO3 required to neutralize the acidity generated from an application of 180 kg N ha-1 y-1.and its subsequent uptake by the plant. The uncoupling of these two processes results in net proton accumulation at one point in the profile and net alkalization at some other point.by the plant at some other point in the profile. Consequently. In contrast. 2003). typical for the NO3. Net Potential acidity generat ed Potential acidity generated from 180 kg N ha-1 a kmoles H+.107 19.kg N Source Urea Diammoni um Phosphate Nitrification reaction (NH4)2CO + 4O2 = 2H+ + 2NO3 . the subsequent leaching of nitrate can result in a significant decline in exchangeable bases because Ca2+ and Mg2+ will move downwards as counter ions for the very mobile NO3-. 1983).0 Amount of CaCO3 required to neutralize acidity generated by an application of 180 kg ha-1 (kg ha-1) 650 0. Estimated potential acidity produced through nitrogenous fertilizers in sugarcane plantations.+ CO2 + H2O (NH4)2HPO4 + O2 = 3H+ + 2NO3 .
Australia.5 pH units).. fence line contrasts of developed and undeveloped sites). 1997).a: Assuming that 1 kmol requires 50 kg CaCO3 to neutralize it. However..2. although little change was noted in the Tully soils where much higher Al % (45%) in both old and new land soils were measured.. The changes included reduced topsoil pH in old land (0. They found that there was no consistent effect of time under sugarcane monoculture on soil chemical properties across sites located in the Burdekin. 2. marked effects were noted at some sites with respect to some soil properties and these were generally consistent with soil acidification. Evidence of accelerated acidification under sugarcane Soil acidification rates can be measured in terms of absolute changes or relative to some control soil. especially in the Herbert where percent Al saturation increased from approximately 5 to 20%. differences in soil chemical properties between new land and land which had been under sugarcane monoculture for more than 20 years were examined in detail by Bramley et al. 1997). decreased cation exchange capacity (CEC) and increased anion exchange capacities (AEC) were found in old land soils at some sites in 10 .1. However. Source: Wood et al. Herbert and Tully Districts of North Queensland. 2003. The use of fence line comparisons essentially results in a conservative estimation of the net acidification rate. 1996. relative rates of acidification can also be derived from survey data (eg. (1996).. either when the distribution of properties through the soil profile. In the former case. 1985. Moody and Aitken. This approach has been used in a number of studies in the sugar industry (Wood. or property values at specific depths were considered. acid addition rates can be estimated from analyses of soils before and after a period of acidification as in long-term studies (Wood et al. increased exchange acidity and aluminium saturation in soils under old land. As part of a wider study on the possible role of changes in soil properties over time on sugar yield decline (Garside et al.5-1. Bramley et al. However. 2003).
has shown that mean topsoil (0-20cm) pHw (pH in 1:5 soil:water) is 4. Wood (1985) obtained similar results in a paired sites study in the Herbert River District. (1996) reported marked differences between South African varieties in terms of their response to lime application suggesting that not only was cane affected by the effects of low soil pH. Australia. lower cation exchange capacity and lower levels of exchangeable base cations (calcium. 1985). North Queensland.each region. assuming that significant leaching occurs (Wood. Schroeder et al. the analysis of soil samples from 1064 sites in the Herbert sugarcane area. However.. magnesium and potassium).28. Schroeder et al. The effects of soil acidification on sugarcane growth have received little attention from Australian researchers. In addition. in Malaysia) Herbert River soil survey (Wood and Bramley. presumably because Hetherington (1986) concluded that cane was tolerant of low pH-induced aluminium toxicity. but that these effects may be variety specific. The contribution to the total proton pool arising from the export of millable cane is relatively small compared to that derived from the nitrification of ammonium and urea based fertilizer sources. Sugarcane soils were found to have a lower pH. (1996) have also reported marked acidification in a range of sugarcane soils in South Africa. most crops perform best when the soil pH is approximately 5. In general. taken as part of the CSR (Central Sugar Refinery.97 and mean subsoil (40-60cm) pHw is 5.0 (Tisdale et al. 1996). 11 . 2003). where he found that many of the differences in soil chemical properties between new cane land and land that had been under sugarcane for several years could be associated with soil acidification. From the previous discussion it can clearly be seen that soil acidification is a continuing problem confronting the Australian sugar industry and that the largest potential acidifying component in a sugar production system is the contribution derived from the use of nitrogen fertilizers (Wood.6 to 6.
There are four general classes of these interactions: specific adsorption. 1995b). 1995b). ionization of metals increases at low pH thereby increasing water solubility and mobility. adsorbs metals by forming chelate complexes with carboxyl groups of the humic substances playing a predominant role (Alloway. 1995b). such as clay. soil organic matter. It is on the basis of this argument that the current research is mainly based upon. 1995b). bioavailable and enhances their mobility. First. Zn and Cr) are strongly correlated with soil organic carbon content (Xue. soil water. Cation exchange is non-specific interaction of metals with negative surface charges on soil minerals. Alloway (1995a). Adsorption of metals from soil water to soil particles is the most important chemical determinant that limits mobility in soils (Alloway. and air within and above soil depends on a variety of chemical factors.2003).. for instance humus. Similarly. Second. 2. sulfide. 1995b). cation exchange. Specifically the anthropogenic heavy metals (Pb. 2001). and organic ligand complexation (Alloway. 2008). co-precipitation. Effects of Physicochemical parameters on heavy metals Chemical conditions in soil are important secondary determinants of heavy metal transport and fate (Alloway.2. Most research on acidification of sugarcane farms has been on sugarcane production with little being done on environmental effect. The case would not different in Kenyan sugar industry since the same agronomic practices for sugarcane are practiced. The organic carbon fraction has a significant influence on heavy metal transport. hydroxonium ions displace most other cations on negative surface charges. Specific adsorption involves partly covalent bonds between the heavy metal with lattice ions on soil particle surfaces. points out that reduction in acidity of soil leads to naturally occurring heavy metals in the soils becoming more soluble. 12 . Co-precipitation involves formation of water insoluble precipitates of metal cations and anions such as carbonate. or phosphate (Alloway. 1995b) including the naturally occurring heavy metals in soils. The importance of interactions between metals and solid phases of soils. This reduces metal adsorption by cation exchange and organic complexation (Ford et al. Cu. Chemical conditions in soil like soil pH are important secondary determinants of heavy metal transport and fate at the application sites (Alloway.
especially in children.1. Soil water contains only about 0. Lead speciation is rather simple and Pb2+ is the dominant soluble form. Thus an increase in dissolved oxygen also increases dissolved metals hence promoting their mobilization (Duinker et al.01-0. Repeated application of these fertilizers leads to accumulation of Pb in the soils followed 13 . It forms a number of highly insoluble precipitates like Pb(OH)2. Most of these problems manifest themselves in animals higher in their food chains hence international bodies have set limits of heavy metal burden and physicochemical parameters which aquatic environments should not exceed.05-0. 2001). 2001).13% of the total soil lead concentration. Lawrence and Brian. are the principal concern for chronic lead exposure (Goyer and Clarkson.. Lead Lead (Pb) is especially prone to accumulation in surface horizons of soil and this has been attributed to its low water solubility within an environmentally relevant pH range which results to very low mobility (Davies. rather than crop contamination. This is due to reoxidation of the metals. Lead is a contaminant in fertilizers (Mortvedt. 1995). up to 1840 mg/kg of Pb (Lawrence and Brian. 1995. Plant uptake factors for lead are low (0. 2001). 2. 1995). 2002). 1982). Below. When heavy metals are introduced into the aquatic systems. 2001). Dietary intakes of 400 to 500 µg/day of Pb dropped to 120 µg/day of Pb with elimination of this practice (Goyer and Clarkson. 1995). Past uses of food and beverage cans with Pb solder led to significant human exposures (Goyer and Clarkson. Therefore any farming activity that increases heavy metal concentrations will automatically reduce dissolved oxygen. some of the problems associated with specific heavy metals and their international limits in domestic water are discussed. Due to past uses of Pb in industrial processes and consumer products like paint and leaded gasoline. is a more likely exposure hazard (Goyer and Clarkson. 2002).10) due to very low water solubility (Davies. Consumption of Pb contaminated soil/food itself.2.There exists a relationship between dissolved heavy metals and dissolved oxygen in water. aquatic animals and plants may bioaccumulate these heavy metals into their system leading to a number of problems. which will make dissolved oxygen level to reduce with increase in dissolved metals. urban soils often contain high Pb concentrations. and PbCO3 (Davies. Pb3(PO2)2. Neurological problems.
The total body burden has been estimated to range between 100 to 400 mg and this increases with age (Tsuchiya. Kenya Bureau of Standards reported that Pb levels in drinking water should not exceed 0. Inorganic salts of Pb are almost insoluble in water except for the acetate.44 mg/day from food and fluids and 0. 1983). Cullen et al. Lead is a dangerous metal once in the body system. Lead is also associated with depression of endocrine functions. Chakraborty et al.. 1968). 1998). meaning that water-borne Pb is minimal because it forms essentially insoluble sulfates and carbonates (Stokinger. nitrate and chloride. 1983). 1981). Other studies by Griggs (1964). which results in aminoaciduria. A report from Snyder et al.. Joint pains otherwise called “Lead arthralgia” are strongly associated with Pb induced gout caused by lead’s interference with uric acid excretion through the kidney (Tsuchiya. respectively. Cullen et al. it is clear that other than deposition in bone and toxic reactions. Nephrotoxicity is most commonly seen in childhood Pb toxicities (Cullen et al. and Vardhani (1986). Lead causes tubular dysfunction. Afterwards in 1998. show that there is tissue response in Ancytlostoma caninum larvae and toxic effect of lead on immuno-physiology in mice.045 mg/day through urine. (1988) discovered that a high degree of abnormalities was found in tissue nucleic acids of rats treated with Pb. particularly the thyroid and adrenal (Tsuchiya. 1977). Lead inhibition of guanine aminohydrolase could also be involved in this (Cullen et al. 1977. 1996).01 mg/day from air and he loses 0. to some extent. From works of Tsuchiya (1977) and Stokinger (1981). 1981). Pb has minimal involvement with metabolism. Once in water bodies Pb can enter the food chain hence affecting human life.1 mg/day through other routes like sweating.by leaching and transportation into water bodies (Stokinger.01 ppm (WHO. 1983). (1975) indicates that the Pb balance for a 70 kg reference man requires an intake of 0. Pb is associated with a high incidence of premature deliveries and 14 . glysuria and phosphaturia. as well as gout (Cullen et al. (1983) also reported that.05 ppm (KEBS. 1977). for instance a study by Fairchild (1978) revealed that a single intra-cardiac injection of Pb acetate caused abnormal Deoxyribonucleic Acid (DNA) and Ribonucleic Acid (RNA) synthesis in mouse kidney.. They gave a value of 120 mg as the total body burden with 11 mg in soft tissues. with ultrastructural changes in the mitochondria.3 mg/day through faeces and 0. 0. Under normal circumstances 300 µg of Pb are ingested daily by an adult while ingestion of at least 600 µg of Pb daily could result in intoxication (Kehoe. 1983). the World Health Organization reported allowable maximum limits of Pb in drinking water as 0. In 1996. Similarly..
2 mg/day are lost through faeces. NAS (1980) and Stokinger (1981) recommended a daily allowance of 10 mg for men and 18 mg for women. including hormones. levels of at least 0. in some. they reckoned that Pb suppresses testicular functions and even causes sterility in men. 11 mg/day and 1. reported that intestinal absorption of iron especially Fe2+.51 mg/day.3 ppm . Intake of excess iron is also dangerous 15 . Iron is an essential mineral hence a component of several cofactors including hemoglobin and cytochromes. Then 0. 2. at least in prokaryotes. For a 50 kg reference woman.3 ppm of iron.6 mg/day as menstrual loss (Snyder et al. Many enzymes require iron for their activity and. They also reckoned that since some of these are enzymes. 1975). It was therefore necessary to determine point sources of this metal in this study for necessary mitigation measures. It was reported by WHO (1998) that in drinking water. there is a relationship between the levels of free Fe2+ and the whole of the cell activity up to the point of initiation of cell division. including losses via urine of 0. is a complicated active process and that the rate of intake is inversely proportional to the state of the body’s iron stores. 1996) reported that safe drinking water should not exceed 0.20 mg/day. According to Hammond and Beliles (1980).03 mg/day airborne intakes.2 ppm and 0. respectively (Neubauer and Wolf. (1975) reported adults iron adsorption to be 30% of total iron uptake. 2004).25 mg/day. Da Silva and Willliams (1991) noted that iron is a major control element which enzymes involved in secondary metabolism require for their activity.3 ppm stain laundry and sanitary ware. Snyder et al. (1975) wrote that the iron balance for a 70 kg reference man is from intake of foods and fluids at 16 mg/day and airborne intake of 0. iron is found in almost every food with higher concentrations in animal tissues than plant tissues. 0.2. it is weakly bound for example with aconitase (Beinert and Kennedy. Snyder et al.. In addition.2 ppm. the values are 12 mg/day from foods and fluids and 0. and through other routes at 0. faeces 15 mg/day. 1989). Iron The Kenya Bureau of Standards (KEBS. Hammond and Beliles (1980). Allowable limits for Fe in drinking water in the UK. urine and other rootes respectively and 0.spontaneous abortions in humans. From the above discussions it is clear that Pb is a dangerous heavy metal whose consumption should be minimized.03 mg/day.2. EU and USA are 0.
although 1 to 2 mg/day could maintain a positive copper balance.2. Furthermore. copper is a component of most vital enzymes. plants and even aquatic animals and therefore it is necessary to monitor the accumulation of this iron in our natural waters to avoid toxicity of it in the higher animals through the food chains. Forbes (1947) found that serious acute poisoning in children can occur following ingestion in excess of 1 g of iron. 1974) despite the fact that O 2 is a neutral symmetric molecule. is 2 to 3 mg/day. Keevil and Mason (1978) observed that copper. Copper Copper is an essential trace element to man and to all vertebrates. in certain complexes can bind O2 and CO reversibly (Lontie and Vanquickenborne. 1981). Cu (I) and Cu (II). As discussed earlier.3. it has been found that Cu+. photosynthesis in plants and the terminal step of mitochondrial respiration and hence Cu influences life support functions like production of red blood cell and carbohydrate synthesis (USEPA. cytochrome oxidase. 16 . together with iron. . 1980). the oxidation-reduction potential governing the relative predominance of these two valence states is sensitive to the nature and steric arrangement of the surrounding ligand (Reinhammar. The normal iron intake for children is 10-20 mg/kg body weights. The metabolism of copper involves a turn over of the copper-containing enzymes. 1980). and amine oxidase. including tyrosinase. Menke’s disease which is a copper deficiency disease. 2. 1979). According to reports by Piscator (1977) and USEPA (1980). 1981). like the low-valence forms of many other transition metals. Its allowable daily intake according to NAS (National Academy of Science. It is largely combined with serum albumin and alpha-globulin ceruloplasmin. iron is found in virtually every food including water. 1980). are the dominating prosthetic metal ions in the electron carrier proteins participating in the biological oxidation of organic substrates by dioxygen. Copper is especially essential in the electron transfer process which also involve iron in hemoglobin. is a disorder in the metabolism whereby there exists an inability to absorb copper (USEPA. In addition. which serve to transport and regulate copper in the body (Stokinger.since signs appear after the carrier has been saturated with free iron in the blood (Stokinger. Copper is a transition metal that has a particular chemical stability and a functional role in electron transfer and oxygen transport proteins as it has two common valence states.
1996). Environmental Protection Agency (1980) and World Health Organization (1998) standard for zinc in drinking water is 5 ppm based on the bitter taste zinc imparts to water at that level. There was an increase in zinc levels at the tap over finished water levels indicating zinc pickup from the pipe and this was attributed to the soft acid nature of Boston's water. Prasad and Oberleas.. A safe level of 3 ppm of zinc in drinking water might make consumers complain about its appearance and taste (WHO. Levels as high as 675 to 2280 ppm in water are emetic (Stockinger. the most sensitive being the brain and liver (USEPA. In the more acidic water of Seattle. The U. 1980.2. Acute copper poisoning can also lead to hemolytic anemia (Finelli et al. Zinc is present in drinking water usually at concentrations much less than 5 ppm although soft waters could have such concentrations from materials used in the distribution systems and house hold plumbing (USEPA. Typically.At high doses. Allowable maximum limits for zinc in drinking water in the UK and USA is 5 ppm (Neubauer and Wolf. These are some of the problems that may arise if copper content is not checked in our domestic waters. 1998). Minor routes of excretion of Cu include sweat. 1981) hence the need to monitor its presence in drinking water and soil. zinc levels in tap water were higher than in the finished water 95% of the time with 10% exceeding the 5 ppm drinking water standard.5 ppm (NAS. From a study of Boston tap water in the United States. The highest reported level in Seattle was 5. 1977). 1977). 1981). Thus zinc participates in many metabolic 17 . copper can also be excreted and the major excretion route for the absorbed copper is the bile. copper is one of the common metallic elements toxic to humans found in polluted environments (Purves. 1980). The taste threshold for zinc in water is 15 ppm. However. urine. levels of zinc were found at up to 1. but this can be decreased by competition with zinc and binding to ascorbic acid and other compounds (Stokinger. Copper is actively absorbed in the stomach and duodenum (Stokinger.6 ppm with a mean of 0. Stokinger. and saliva (USEPA. 2. Zinc is ubiquitous in mammalian tissues and is involved in the activity of many enzymes. 1990. however. Zinc Safe drinking water should not exceed 5 ppm of zinc (KEBS. 1981). 1981). 2004). 1981). 1976).2 ppm (NAS. Wilson's disease is due to inability to utilize copper and is a hereditary metabolic disorder whereby there is accumulation of copper in some organs of the body. 1977). about half of the ingested dose is absorbed.4.S.
Found in air. Action of stomach digestion tends to change Cr6 to Cr3. The above discussed problems can therefore be minimized if proper mitigation measures are taken to control the source. bound mainly to albumin and in the serum. cell division and growth. 1980). and DNApolymerase (Taylor et al. 2. carbonic anhydrase.processes (USEPA. Absolute amounts required range from 1. Considered by the USEPA to be a carcinogen. It is found in foods such as cole crops. 2003). 2003).. soil and some foods. including steel making. Zinc is essential in enzyme and enzymatic functions such as DNA.1 mg/day in infancy. Excessive Zinc intake has been associated with copper deficiency anemia for it interferes with copper and iron metabolism (USEPA.. Chromium Chromium usually appears commonly in the environment as a trivalent salt Cr-III or Cr3+ (ATSDR.55 to 3.0 mg/day in pregnancy.8 mg/day at puberty. 18 . 1980). tanning. It is essential for spermatogenesis. 2. RNA and protein synthesis. 1995) and hence its continued use may lead to accumulations at the application sites.5. 2003). carboxy peptidases. Thymidinekinase is also zinc dependent (USEPA. and textiles (ATSDR. RNA-polymerase. and can lead to ulceration of the liver and nasal septum (ATSDR. (2003). 2. brewer’s yeast and cereal grains ATSDR.2. It is also essential in carbohydrate metabolism. leucine aminopeptidase. in several zinc metalloenzymes in the plasma. It is therefore important to monitor zinc levels in drinking water so as to prevent problems that arise due to its toxicity. and foetal nutrition. It is also involved in pituitary and adrenal gland metabolism (USEPA. 1980). in the leucocytes..2 mg/day in child hood and adult hood. it is an essential trace element. 2003). 1982). plating. (Cr-VI or Cr6+) is readily absorbed by the body. 2003). 1982). 1982). Zinc is also essential for the activity of the following enzymes: alcohol dehydrogenase. Zinc is present in the erythrocytes as the zinc metalloenzyme carbonic anhydrase. aiding in the metabolism of carbohydrates etc (ATSDR.45 mg/kg body weights during lactation (Taylor et al. bound to a macroglobulin and to amino acids (Taylor et al. alkaline phosphatase. ova formation. but Cr6 is a strong oxidizer and can damage cell walls easily (ATSDR. 1980). Hexavalent Chromium (Cr VI) is the byproduct of industrial applications. water. and 5. Zinc is a pollutant in most commercial fertilizers (Mortvedt. utilization of nitrogen and sulfur. 2.
a lower ability to fight diseases. According to Dennis et al. Cary et al.and dichromate (Cr2O2-7) with CrO2-4 the predominant form at pH> 6 (Alloway. Chromium (VI) is a danger to human health because it can alter genetic materials and cause cancer (Cheryl and Susan. 2000). chromium causes respiratory problems.g. tannery wastes. 2000). infertility and tumor formation. 2000). The soil maintains small amounts of Cr (III) in solution above the pH at which uncomplexed Cr precipitates and is therefore a means of enhancing its mobility (Bartlett and James 1988). However. 1977). leather by-product. is much less mobile and adsorbs to particulates more strongly. Chromium attaches tightly to soil particles. fulvic acids and soil extracts of water-soluble organic matter). Cr (VI). Chromate (CrO2-) is in pH dependent equilibrium with other forms of Cr (VI) such as HCrO4. 1995a). the relatively insoluble and less mobile Cr (III) form predominates and it generally occurs as insoluble hydroxides and oxides (Cary et al. Chromium (III) is an essential nutrient for humans and shortages may cause heart conditions. The solubility of Cr (III) decreases above pH 4 and above pH 5. Excess chromium (III) causes negative health effects for instance skin rashes (Cheryl and Susan. 1995a).. Chromium may exist in a number of oxidation states. These have sharply contrasting chemical properties: Cr (IV) exists as an anion.. only a small part of the chromium that ends up in water will eventually dissolve. 1977). but the most stable and common forms are Cr (III) and Cr (VI). it is more readily extracted from soil and sediment particles and is considered the more toxic form (Alloway 1995). citric acid. Following reduction of Cr (VI).5 complete precipitation occurs (Alloway. disruptions of metabolisms and diabetes (Cheryl and Susan. is a strongly oxidizing species. It is therefore important to monitor it in the environment. 1995a). Bartlett and Kimble (1976) 19 . Furthermore from his work. Chromium (III) on the other hand. (1977) observed that additions of soluble Cr as either Cr (VI) or Cr (IlI) to soils reverted to forms which were insoluble and unavailable to plants. Thus in the majority of soils. Chromium (VI) is the more stable form in equilibrium with atmospheric oxygen. with its high positive reduction potential. and the usual exposure pathways are due to exposure to dusts and sediments (ATSDR. For example. Reduction is more rapid in acid than alkaline soils (Cary et al.Sources of Cr6+ in the Rivers and streams include steel manufacturing. it was concluded that insoluble Cr in the soils was present as hydrated oxides of Cr (IlI) complexing with soluble organic acids (e. 2003). 2003). birth defects. and sewage sludge (ATSDR. and in the presence of soil organic matter Cr (VI) is reduced to Cr (III) (Alloway. (2003).
the soil pH is lowered by drying (Bartlett and James. Phosphates are classified as orthophosphates (PO43-. organic phosphates are biologically transformed back to orthophosphates. In situations where the Cr (VI) form remains in soil. 1988) In essence. 1995). 1995). 1988) 2. Primarily biological processes contribute to formation of organic phosphates (Clark and John.3. Polyphosphates enter sewage water through wastes and food residues (Alloway. 1991). Like polyphosphates. Phosphates are typically present in raw wastewaters at concentrations 20 . Orthophosphates in an aqueous solution can be used for biological metabolism without further breakdown (Clark and John. although there are difficulties in detecting the transition because drying and storage seemingly destroy the capacity of soil to oxidise the element (Bartlett and James. 1991). condensed phosphates or polyphosphates. 1988).and Bartlett and James (1988) drew attention to the similarity of adsorption and solubility behavior between Cr(III) and Al(III) in response to changes in pH and phosphorus status of soils.and H3PO4). which are molecules with two or more phosphorus atoms. Physicochemical parameters and their environmental impact Phosphorus is essential to the growth of biological organisms. In fact. Bartlett and James (1979) found that the amount of Cr (IlI) oxidised to Cr(VI) was proportional to the Mn reduced and also to the amount reducible by hydroquinone. Orthophosphates applied to agricultural or residential cultivated land as fertilizers may be carried into surface waters with storm runoff and melting snow (Franson. Bartlett and Kimble (1976) contend that its adsorption capability is similar to that of orthophosphate and the anion will remain mobile only if its concentration exceeds both the adsorbing and the reducing capacities of the soil. 1991). 1991). oxygen atoms and in some cases hydrogen atoms combined in a complex molecule with organically-bound phosphates (Clark and John. 1991). They may also be formed from orthophosphates in biological treatment processes and by receiving water organisms (Clark and John. HPO2. 1995c). Phosphorus occurs naturally in bodies of water mainly in the form of phosphates (Clark and John. including both their metabolic and photosynthetic processes. Polyphosphates slowly undergo hydrolysis in aqueous solutions and are converted to the orthophosphate forms (Franson. Oxidation of a proportion of Cr (III) is considered a likely occurrence in soils with a pH greater than 5 and rich in oxidized Mn. adsorption of Cr(VI) in certain soils can offset its reduction (Bartlett and James.
near 10 mg/L as P (Richard, 1991). During wastewater treatment, about 10-30% of the phosphates in raw wastewater is utilized during secondary biological treatment for microbial cell synthesis and energy transport (Richard, 1991). Additional removal is required to achieve low effluent concentration levels from the wastewater treatment process. Effluent limits usually range from 0.1-2 mg/L as P, with many established at 1.0 mg/L (Richard, 1991). Removal processes for phosphates from wastewaters involve incorporation into suspended solids and the subsequent removal of those solids (Richard, 1991) which form sludge and finally biosolids. Rainfall can cause varying amounts of phosphates to wash off from farm soils into nearby waterways. Phosphate will stimulate the growth of plankton and aquatic plants which provide food for fish (LVEMP, 2003). This may cause an increase in the fish population and improve the overall water quality (LVEMP, 2003). However, if an excess of phosphate enters the waterway; algae and aquatic plants will grow wildly, choke up the waterway and use up large amounts of oxygen (LVEMP, 2003). This condition is known as eutrophication or over-fertilization of receiving waters. This rapid growth of aquatic vegetation eventually dies and as it decays it uses up oxygen. This process in turn causes the death of aquatic life because of the lowering of dissolved oxygen levels (LVEMP, 2003). The addition of phosphates through the activities of humans can accelerate the eutrophication process of nutrient enrichment that results in accelerated ecological aging of lakes and streams (LVEMP, 2003). Phosphorus, especially in inland waters, is often the nutrient that limits growth of aquatic plants. Critical levels of phosphorus in water above which eutrophication is likely to be triggered are approximately 0.03 mg/L of dissolved phosphorus and 0.1 mg/L of total phosphorus (USEPA, 1980). The discharge of raw or treated wastewater, agricultural drainage, or certain industrial wastes that contain phosphates to a surface water body may result in a highly eutrophic state, in which the growth of photosynthetic aquatic micro and macro organisms are stimulated to nuisance levels (Richard, 1991). Aquatic plants like water hyacinth and mats of algal scum may cover surface water (LVEMP, 2003). As these algal mats and aquatic plants die, they sink to the bottom, where their decomposition by microorganisms uses most of the oxygen dissolved in the water. The decrease in oxygen severely inhibits the growth of many aquatic organisms, especially more desirable fish and in extreme cases may lead to massive fish 21
kills (Richard, 1991). Excessive input of phosphorus can change clear, oxygen-rich, good-tasting water into cloudy, oxygen-poor, foul smelling, and possibly toxic water. Therefore, control of the amount of phosphates entering surface waters from domestic and industrial waste discharges, natural runoff, and erosion may be required to prevent eutrophication in water bodies and the nucleus estate farms of Nzoia have been suspected to be one of the point sources of phosphates from nitrogenous fertilizer application that needs to be known. Nitrates and nitrites are families of chemical compounds containing atoms of nitrogen and oxygen. Occurring naturally, nitrates and nitrites are critical to the continuation of life on earth, since they are among the main sources from which plants obtain the element nitrogen. This element is required for the production of amino acids, which, in turn, are used in the manufacture of proteins in both plants and animals (Franson, 1995). One of the great transformations of agriculture over the past century has been the expanded use of nitrogenous fertilizers and biosolids. Ammonium nitrate is one of the most important of these fertilizers (Alloway, 1995b). In recent years, this compound has ranked in the top fifteen among synthetic chemicals produced in the United States (Richard, 1991). The increased use of nitrates as fertilizer has led to some serious environmental problems. All nitrates are soluble, so whatever amount is not taken up by plants in a field is washed away into surface water and eventually into rivers, streams, ponds, and lakes. In these bodies of water, the nitrates become sources of food for algae, water hyacinth and other plant life, resulting in the formation of algal and hyacinth blooms as is the case of Lake Victoria (LVEMP, 2003). Such blooms are usually the first step in the eutrophication of a pond or lake (Fried et al., 2003; LVEMP, 2003). Furthermore, some scientists believe that nitrates and nitrites may themselves be carcinogens or may be converted in the body to a class of compounds known as nitrosamines, compounds that are known to be carcinogens (Richard, 1991). Total oxidized nitrogen is the sum of nitrate and nitrite nitrogen. Nitrate generally occurs in trace quantities in surface water but may attain high levels in some groundwater (Richard, 1991). In excessive amounts, it contributes to the illness known as methemoglobinemia in infants hence the limit of 10 mg nitrate-nitrogen/L being imposed on drinking water to prevent this disorder (USEPA, 1980).
The contamination of the water systems with inorganic nitrogen and phosphorus from nitrogenous fertilizer runoff is a pressing concern given their prevalence in agricultural application in the Nzoia Sugar Company nucleus estate farms. To maintain a healthy hydrologic network, it is necessary to understand the effects of these increased chemical concentrations on water quality. Previous studies have shown that the addition of these nutrients to the water system would result in large proliferations of algae and water hyacinth, which have detrimental effects on the water quality (Fried et al. 2003; LVEMP, 2003). Algal blooms and water hyacinth deplete the oxygen supply in the water system and are harmful to other aquatic species (LVEMP, 2003). Additionally, these nutrients cause taste and odor problems that result in reduced recreational use, and increased water treatment costs (Fried et al., 2003). In an effort to maintain a healthy water system and to minimize algal growth, USEPA (1980) recommends that phosphate levels be kept below 0.1 mg/L and nitrate levels be kept below 10 mg/L. Furthermore Zwolsman et al. (1997) reported that dissolved metal behavior is influenced by redox chemistry and nitrate is a fair measure of redox condition in water. Also his reckoning that there is interplay between favorable redox conditions indicated by NO3-and low pH values which all lead to high concentrations of dissolved metal is well noted. Dobermann and Fairhurst (2000) reported that the ammonium form of nitrogen is rapidly converted to the nitrate form during nitrification and that nitrification has a net acidifying effect on soil (Table 2.1). Adequate oxygen levels are necessary to provide for aerobic life forms which carry on natural stream purification processes (Hutchinson, 1957). As DO levels in water drop below 5.0 mg/L, aquatic life is put under stress (Hutchinson, 1957). The lower the concentration, the greater the stress (Hutchinson, 1957). Oxygen levels that remain below 1-2 mg/L for a few hours can result in large fish kills (Tchobanoglous and Shroeder, 1985). Fish in waters containing excessive dissolved gases may suffer from "gas bubble disease"; however, this is a very rare occurrence. The bubbles or emboli block the flow of blood through blood vessels causing death (Tchobanoglous and Shroeder, 1985). Aquatic invertebrates are also affected by gas bubble disease but at levels higher than those lethal to fish (Tchobanoglous and Schroeder, 1985). There also exists a direct relationship between DO in water and dissolved heavy metals (Duinker et al. 1982). Duinker et al. (1982) writes that this is due to reoxidation of the metals that make DO consequently reduce with increase in dissolved heavy metals.
Electrical Conductivity is a measurement of the ability of an aqueous solution to carry an electrical current. It is used to determine mineralization which is commonly called total dissolved solids. Total dissolved solids information is used to determine the overall ionic effect in a water source (http://kywater.org/ww/ramp /rmcond.htm 9/15/2009 4:59 pm). Certain physiological effects on plants and animals are often affected by the number of available ions in the water. Elevated dissolved solids can cause "mineral tastes" in drinking water. Corrosion or encrustation of metallic surfaces by waters high in dissolved solids causes problems with industrial equipment and boilers as well as domestic plumbing, hot water heaters, toilet flushing mechanisms, faucets, and washing machines and dishwashers (http://kywater.org/ww/ramp /rmcond.htm 9/15/2009 4:59 pm). Water quality criteria have been established only for the mainstream of the Ohio River. The limit is 800 µohms/cm or 500 mg/L total dissolved solids. (http://kywater.org/ww/ramp /rmcond.htm 9/15/2009 4:59 pm). Chemical oxygen demand (COD) is a measure of the capacity of water to consume oxygen during the decomposition of organic matter and the oxidation of inorganic chemicals such as ammonia and nitrite. Measurements of COD are commonly made on samples of waste waters or of natural waters contaminated by domestic or industrial wastes. Chemical oxygen demand is measured as a standardized laboratory assay in which a closed water sample is incubated with a strong chemical oxidant under specific conditions of temperature and for a particular period of time (David, 2006). A commonly used oxidant in COD assays is potassium dichromate (K2Cr2O7) which is used in combination with boiling sulfuric acid (H2SO4) (David, 2006). Because this chemical oxidant is not specific to oxygen-consuming chemicals that are organic or inorganic, both of these sources of oxygen demand are measured in a COD assay (David, 2006). Chemical oxygen demand is related to biochemical oxygen demand (BOD), another standard test for assaying the oxygen-demanding strength of waste waters. However, biochemical oxygen demand only measures the amount of oxygen consumed by microbial oxidation and is most relevant to waters rich in organic matter (David, 2006). It is important to understand that COD and BOD do not necessarily measure the same types of oxygen consumption. For example, COD does not measure the oxygenconsuming potential associated with certain dissolved organic compounds such as acetate. However, acetate can be metabolized by microorganisms and would therefore be detected in an assay of BOD (David, 2006). In contrast, the oxygen-consuming potential of cellulose is not measured during a short-term BOD assay, but it is measured during a 24
Chemical Oxygen Demand≤/a> 8/15/2009 3:50). In conclusion, use of nitrogenous fertilizers in sugarcane farming affects soil acidity. No work has been done in Nzoia Nucleus estate farms on the effect of this acidity on availability, solubility and mobility of heavy metals. Apart from bioaccumulation in aquatic animals and plants, presence of bioavailable heavy metals in aquatic environments is correlated with and affects other physicochemical parameters like dissolved oxygen, chemical oxygen demand and conductivity which in turn will affect the aquatic environment. There is therefore need to monitor these physicochemical parameters and heavy metals before serious health and environmental problems arise from intensive farming activities and nitrogenous fertilizer application in large scale farming systems such as Nzoia sugarcane farms.
Chapter 3 Materials and methodology 3.1. Study area
The study area was the nucleus of Nzoia Sugar Company Limited that is located in Bungoma District, Western Province and is within Kenya’s sugar belt. It lies between 34º 50’49”E-35º 35’41”E longitudes and 0º4’55”N-0º20’11’S latitudes. There is heavy 25
During the rains several canals carry with them residues of chemicals that may be changing physical chemical parameters of water and causing accumulation of heavy metals in River Kuywa. The nucleus farms have black nitrosol soils that are deep and well drained (DDP. Most of the rainfall is received during the long rain season which is from April to June while the short rains season is from September to November (Table 1. which is a tributary to River Nzoia that drains its water into Lake Victoria. farms and at three points along River Kuywa as shown in Figure 3. which passes within the nucleus estate farms. The factory draws water from River Kuywa.2) while plot 8071 was chosen due to its use as a dump site.1) and the annual temperature ranges from 15oC minimum to 30oC maximum (DDP.1). Sampling plots were chosen out of their history in nitrogenous fertilizer applications (Table 1. DDP. a canal 26 . specifically Kanduyi District Education Board Primary School football pitch which lies within the same geographical region as Nzoia Sugar Company) was chosen as a control for soil analysis. and discharges back its effluent to the same river downstream before it joins River Nzoia. Sampling and sampling design Two factor completely randomized block design was used in sampling where the nucleus estate farms were considered as a block and sampling sites located within the nucleus’ canals. 3. 1996. In all the sampled plots. A point in the river (sampling a in the river) before it enters the nucleus was chosen as a control for the river samples and a canal (sampling 1 in plot number 9053) that originated from a tree plantation within the nucleus was chosen as a control for the canals (Figure 3. 2002).2).1 and 1. 1996). the canals do not dry up.sugarcane farming in the nucleus farms where nitrogenous fertilizers such as Diammonium phosphates (DAP) and urea are applied during the onset of the long rains (Table 1. Although the water volume within the canals drops during the dry season and increases during the wet season. These canals contain perennial water that flows within the nucleus estate farms and are linked to River Kuywa.2.1 in order to give trends of analyte levels and to establish potential point sources. A site outside the nucleus where there is no farming (a football pitch within Nzoia sugar belt.
For water and sediment sampling. 3. Surface sediment and top soil samples were dried at room temperature then ground by a pestle and motor in order to normalize for variations in grain size distribution. four 15cm deep top soil samples in black plastic bags using a big spoon and PVC pipes (1. Sampling and Sample preparation before extraction Four 500 ml of surface water samples were taken from each sampling site in glass bottles.89’’E 0o 36’ 14.3. 34o 39’ 03.49’’E 34o 42’ 15.15/3/2009 and wet season . in the middle or next to them. Four samples each measuring 100 g of each type of fertilizers used namely DAP and Urea were picked at random from the 50 bags of fertilizers sampled at random in the nucleus stores and kept in plastic bags ready for analysis Once collected.24’’N Factory Sewage treatment Sampling a in River Kuywa (control) Sampling point 7 Sampling point 2 27 Sampling Sampling on point b point 3 Kuywa River .21/5/2009. Sampling was done during the dry season . in each one of the sampling sites per trip were taken. a shallow point (approximately 2 m into the river and in the middle of the canal). respectively.24’’N 34o 40’ 47. Water samples were acidified using 1 ml of concentrated nitric acid and stored at 4 oC to preserve them as processing continued (Nichole and Mason. the surface water samples were transported in an icebox at 0oC to the laboratory for storage and processing while surface sediments and top soils were kept in black plastic bags and transported to the laboratory for analysis. river bank left and river bank right were pooled and treated as one sampling site whereby three samples were collected and treated as triplicates with one back up. four 100 g samples of surface sediments. Soil was sampled in the farm while water and sediments from the canal and River Kuywa as shown below. The samples were then sieved through a 45 µm mesh sieve and kept in clean plastic containers ready for processing. Fertilizer samples were dried at room temperature and ground in a pestle and motor in order to normalize for variations in grain size distribution.passed near. 2001).90’’E 0o 36’ 14. They were then sieved through a 45 µm mesh sieve and kept in clean plastic containers ready for analysis.5cm in diameter).
17’’N o Sampling point 4 Sampling point c on River Kuywa 34o 39’ 03. a – c: sampling points in River Kuywa.89’’E 0o 31’ 34. A sketched map of Nzoia Sugar Company Nucleus estate farms and sampling points.0o 34’ 19.17’’N Key Sampling point: 1 (A) . 3 (C) .84’’N Sampling point 6 Sampling point 5 0o 32’ 44.29’’N 0o 32’ 44.Plot 429. cooled in a desiccator and weight measurement taken before being put in a 50 ml Pyrex digestion tube and 10 ml mixture of concentrated nitric acid 28 .Plot 125.1. A mass of one gram of sediment was dried in an oven at 104oC.Plot 8071.Plot 9053.4. : Canals.Plot 243. top soils and fertilizers Total surface sediment extractions were carried out according to the procedure of Tack and Verloo (1999) with slight modifications. 1 – 7: sampling points for canals. Determination of heavy metals in surface sediments.49’’E 34o 42’ 15. 7 (G) . 6 (F) .84’’N Sampling 1 (control) 0o 34’ 19.29’’N 0 31’ 34.90’’E 34o 40’ 47. Kuywa River A – G: Sampling points for soil in the indicated plots. 3. 5 (E) . Figure 3. 2 (B) . 4 (D) .Plot 413. Sampling 1 – control for the canals (a canal drawing its water from a tree plantation).Plot 616.
8 nm. 1965). The samples were acidified to 1% (2 ml) with conc. copper sulphate.. lead nitrate. Ongeri.and concentrated hydrochloric acid (4:1. 100 µg/L. the AAS machine was calibrated.3 nm were used to measure absorbances of Pb.5 mg/ml of strontium chloride.6H2O). 357. Determination of heavy metals in water The procedure adopted by Mzimela et al. 20 µg/L. The evaporated sample was transferred to a 29 . 324. nitric acid (AR). (2003) for total metal extraction was followed. aqua ragia digestion) added.8 nm. the contents were filtered through 0. Before analysis was done.5 mg/ml of strontium chloride (analytical grade. Salts of potassium dichromate. respectively (Berman. The same procedure and that of Alloway (1995a) were adopted for both fertilizer and top soil samples with slight modifications. Cu. 40 µg/L. Wavelengths of 283. 1986.3 nm. 160 µg/L and 250 µg/L per salt in 100 ml flasks after additions of 1.9 nm. The extract was analyzed for Pb. Cr. These salts were used as standards and a calibration curve was drawn from them in the instrument before unknown samples were read. 2008). 120 µg/L. zinc nitrate and iron nitrate were used to prepare known concentrations of 0 µg/L. Cr. Zn. The purpose of strontium chloride was to remove interference in absorption of the specific metal by other metals at the same wavelength by acting as a buffer and to minimize ionization of the metal atoms (Ikuo et al. SrCl2. Zn and Fe. 80 µg/L.45 µm polyethersulfoon filter membrane into a 50 ml volumetric flask and made up to volume with double-distilled water after addition of 1.5. A water sample measuring 200 ml was filtered through a 1 µm cellulose acetate filter with mill pores into an acid-washed 500 ml Erlenmeyer flask. and Fe using Shimadzu AA-6200 Atomic Absorption Spectrophotometer with their respective Hamatsu hollow cathode lamps. placed on a hot plate at 60oC and allowed to evaporate to approximately 30 ml. 3. and 243. Following digestion for 3 hours in a Gerhardt digester at 100oC. Cu. 213.
Salts of potassium dichromate.50 ml volumetric flask and made up to volume with double distilled water after addition of 1.9 nm. respectively (Berman.8 nm. 324.5 mg/ml of strontium chloride. For soil pH a method adopted from Rhodes (1982) was used. copper sulphate. 100 µg/L.3 nm. 40 µg/L. Temperature. ammonium 30 . A digestion method with HNO3-H2SO4 was necessary to oxidize organic-bond P by rupturing both C-P and C-O-P bonds and releasing P as soluble PO43-. 20 µg/L. then the pH measured using a pH meter (3071 Jenway). 80 µg/L. 357. and 243. Before analysis was done.5 mg/ml of strontium chloride.7. lead nitrate. 1986. The total phosphate content of a water sample includes all of the o-phosphates and condensed phosphates. Wavelengths of 283. In a dilute o-phosphate solution. Cu. Zn and Fe. whereby 50 ml of deionized water was added to 20 g of crushed soil. Cr. Turbidity and Electrical conductivity Water pH and temperature were measured directly in the field using a pH meter (3071 Jenway) and a mercury thermometer. Cu. CG 857) respectively.3 nm were used to measure absorbances of Pb. 3. and Fe using Shimadzu AA-6200 Atomic Absorption Spectrophotometer with their respective Hamatsu hollow cathode lamps. Determination of total phosphates A method as described by Anil (1994) for total phosphates was adopted. both soluble and insoluble and organic species.8 nm. The extract was analyzed for Pb. Cr. Measurement of pH. the AAS machine was calibrated. stirred well for ten minutes and allowed to stand for 30 minutes before stirring again for two minutes. 3. 2008). 160 µg/L and 250 µg/L per salt in 100 ml flasks after additions of 1. 120 µg/L. These salts were used as standards and a calibration curve was drawn from them in the instrument before unknown samples were read.6. Turbidity and Electrical conductivity were measured insitu using a turbidity meter (Hanna instruments Hi 93703 microprocessor turbidity meter) and electrical conductivity meter (Konduktometer. Zn. 213. Ongeri. zinc nitrate and iron nitrate were used to prepare known concentrations of 0 µg/L. respectively.
Armstrong. The residue was leached with 5 ml 1 N HNO 3 and transferred to a 50 ml volumetric flask. Potassium nitrate (KNO3) was dried in an oven at 105°C for 24 hours then 0. Navone 1964). The latter reacts with vanadium to form yellow vanadomolybdophosphoric acid which is measured at 460 nm. Determination of Nitrate-Nitrogen Ultraviolet spectrophotometric screening method of Franson (1995) was used to determine nitrate–nitrogen present in the filtered water samples.molybdate reacts in acidic medium to form molybdo-phosphoric acid. Goldman and Jacobs.value. Shimadzu) machine yellow reaction vanadomolybdophosphate. Acidification with 2 ml of 1 N HCl was designed to prevent interference from hydroxide or carbonate concentrations of up to 1000 mg CaCO3/L.7218 g dissolved in water and diluted to 1000 ml to make a nitrate stock solution. A calibration curve was prepared and total concentration of phosphates per litre determined. 220 g KH 2PO4/L. Chloride has no effect on the determination (Ioather and Rackman. Measurement of UV absorption at 220 nm enabled rapid determination of NO3-. The mixture was diluted to the mark with distilled water and left to cool for 10 minutes. Double distilled and deionized water of highest purity was used to prepare all solutions and dilutions. Absorbance was measured using an ultra violet spectrophotometer of the (UV-1650 PC-UV-Vis product.25% ammonium vanadate in 6 N HCl. 1963. spectrophotometer. A volume of 100 ml of water sample in a beaker was digested at 150oC with 1 ml concentrated sulfuric acid (H2SO4) + 5 ml concentrated nitric acid (HNO3) and evaporated to dryness. 31 . 3. Absorbances of a blank and calibration standards that were prepared from solutions of phosphate. Then a volume of 100 ml stock nitrate solution was diluted to 1000 ml with double distilled water to make intermediate nitrate solutions for calibraton.does not absorb at 275 nm. 1961. Because dissolved organic matter also may absorb at 220 nm and NO3. A volume of 5 ml of 10% ammonium molybdate was added followed by addition of 5 ml of 0.8. Sample filtration was intended to remove possible interference from suspended particles. 1959. at 460 nm. 1 ml = 50 µg PO4 carried through the same steps were measured. a second measurement made at 275 nm was used to correct the NO 3.
After two hours the samples were cooled and put in 50 ml flasks ready for analysis. In this method. Shimadzu). The machine (UV-1650 PC-UV-Vis spectrophotometer. Solids that adhered to container wall were dislodged 32 . Shimadzu) was calibrated using standards of NO3-N prepared in the range of 0 to 7 mg NO3-N /L by diluting to 50 ml the following volumes of intermediate nitrate solution: 0. and standards were inverted several times and solids allowed to settle before measuring absorbance.216 g of K2Cr2O7. then 167 ml of conc. 4. previously dried at 103oC for 2 hours was added. Determination of Chemical Oxygen Demand Closed Reflux colorimetric method described fully in standard methods of Franson (1995) was adopted. H2SO4 and 33. The samples were treated by taking 5.9. Using corrected sample absorbance.3 g of HgSO4 added and dissolved before cooling to room temperature and diluting to 1000 ml in order to make a digestion solution. technical grade. In calculating the NO3-N values. The standards were treated in the same manner as samples. 3. and 7. Potassium hydrogen phthalate (HOOCC6H4COOK) was used as a standard.00. H2SO4 at the rate of 5. Absorbance against redistilled water set at zero absorbance were read using a wavelength of 220 nm to obtain NO3-N reading and a wavelength of 275 nm to determine interference due to dissolved organic matter (UV-1650 PC-UV-Vis spectrophotometer. sample concentrations were determined from the standard curve.0 ml sulfuric acid so that an acid layer was formed under the sample and the digestion solution layer and mixed thoroughly.00. Ampule tubes were placed in a block digester preheated to 150oC and refluxed for two hours. blank.0 ml of water sample into a digestion vessel and 3.00. 10.5 g Ag2SO4/kg H2SO4 and left to stand for a day in order to dissolve so as to make a sulfuric acid reagent.Samples measuring 50 ml were filtered and 1 ml concentrated HCl solution added and mixed thoroughly.00 ml. A blank and four standards were prepared in the same manner. two times the absorbance reading at 275 nm was subtracted from the reading at 220 nm to obtain absorbance due to NO3-N. was added to conc. A powder of Ag2SO4. A standard curve was constructed by plotting absorbance due to NO3-N against NO3-N concentration of standard. primary standard grade.0 ml of digestion solution added followed by careful addition of 7. for samples and standards. 1. 2. Cooled samples. to 500 ml distilled water.
A fast quantitative reaction was ensured by addition of Mn(II) salts in strongly alkaline medium: Mn2+ + 2. tube... or ampule size. (2002)..0 g NaN3 diluted to 1 L...025 M Na2S2O3 ≡ 1 mg L-1 DO (Anil. Determination of Total Organic Carbon A method. 300.+ S4O62.11....10. The mixture was shaken well until the precipitate dissolved.→ 2I.... same reagent volumes were used. and digestion procedure followed as for the samples and COD calculated as mg O2/L = (mg O2 in final volume x 1000) / ml sample 3.. in which DO was allowed to react with I . and 2 ml of 36% MnSO4 plus 2 ml of alkaline iodide-azide solution (50 g NaOH + 13.... which was then titrated with standard Na2S2O3 solution. In preparing the calibration curve..eq 3 5 ml of 0.. at least eight standards from potassium hydrogen phthalate solution with COD equivalents of 20... Analysis of Dissolved Oxygen (DO) The Winkler method as outlined by Anil (1994) was used to analyze dissolved oxygen. In this method 10 g of well mixed air dried sample was heated in an oven 33 .....solution.eq 2 I2 +2S2O32...and SO32...5 g NaI + 1...eq 1 (the oxygen in the equaton is the one dissolved in water) MnO2 + 2I.5O2 →2 MnO2 ↓ + H2O . was used to determine total organic carbon...by gentle tapping and settling...025 M Na2S2O3 solutions (eqn 3) and the results calculated: 5 ml of 0... 100. Volume was made to the mark with distilled water..... The mixture was shaken well and the precipitate allowed to settle then 6 ml of 12 N H2SO4 added (eq 2).. 1994) 3.... Absorbance was compared to a calibration curve by the machine and concentrations of unknown samples read directly..) was also added (eq 1).. 2 ml of 40% potassium fluoride (KF) (to mask Fe3+) was added. The liberated iodine was titrated with 0.... (Interference due to oxidizing agents such as NO2. 500..to form I2. 700 and 900 mg O2/L were prepared...+4 H+→Mn2+ + I2 +2H...025 M Na2S203 ≡ 1 mg L-1 DO A volume of 50 ml of sample was put in a 250 ml bottle.. Absorbances were measured using a spectrophotometer (UV-1650 PC UV-Vis spectrophotometer Shimadzu) set at 600 nm... as described by Okalebo et al....present in waste water ware eliminated by addition of NaN3 to alkaline I.
1.dry season and 2 – wet season) and Factor B (SITE) with values from 1 to 7 for soil and canals. 3. physicochemical parameters n water. to 550°C then maintained at 550°C for eight hours.05) were used to check the variations. Factor A (SEASON) with values from 1 to 2 (1. thus heavy metals in water and sediments.for 3 hours at 105°C in a crucible and the difference in weights noted as the moisture content. Analysis of variance (ANOVA) (p ≤ 0. Chapter 4 Results and Discussion 4. Statistical analysis was performed using MSTATC two factor completely randomized design. With factorial ANOVA for the factors such that Replication was with values from 1 to 3. The grayish white ash sample was then removed and cooled in a desiccator.12.05) (two factor experiment) and students T-test (p ≤ 0.05) obtained from the t-distribution table. The LSD values were calculated using the formula: √2 × s/y × t whereby s/y value was given by the ANOVA program results and t is the significant level (P ≤ 0. Statistical analysis The means and ranges of the data collected were determined in this study. then weighed. The difference in weight between the moisture free sample and the ash represented the total organic carbon of the sample. Nucleus soil analysis and fertilizer analysis. Confidence limit of 5% was applied to test the significance of the analytical results. The sample was then placed in a Vulcan A-550 muffle furnace in a crucible and the temperature raised slowly from 100. The results have been presented in four categories. 200. Nucleus Soil Analysis 34 .
46 5.46 7.The results for nucleus soil analysis are recorded in Tables 4.1.014 and from the control site was 1.35 5.89 Site mean 8.00 5.003 ng/mL.79 0. Pb.05 6. 0.76 5.92 4. Mean Total Organic Carbon (%) in soils from the nucleus and from a control farm within Nzoia sugar belt Sites (in plot numbers from the nucleus and a control farm) A.5 7.39 Control x 7. 0.25 5.6.27 Control z 121.34 6.34 118.28 8. 94.46 7.001 ng/mL.2 120. 89.95 171.10 5.79 Control z 4.08 90.48 D (125) 9. (9053) B (8071) 130. 0.05 6.58 154. respectively.29 130.34 5.85 Control y 122.61 Interaction CV% 0.76 C (243) 6.35 6.2.68 9. Zn and Fe as 93.05 175. 88 and 84.74 F (429) 178. Control xyz: Soil samples taken from a football pitch of Kanduyi primary school within Nzoia sugar belt.029 ± 0.18 4.62 E (616) 143.967 Key: A – G: Soil sampling points in the indicated plots as illustrated in figure 3.94 0.33 Control mean 7.71 D (125) 184.08 5.1.288 33. (9053) B (8071) 5.89 Dry season Wet season Mean Lsd P≤ 0.08 G (413) 5.05 130. Mean site variations of heavy metals in top soils from the nucleus of Nzoia Sugar Company and a control farm between the long wet and dry seasons. Mean site variations of selected physicochemical parameters and heavy metals in top soils from the nucleus of Nzoia Sugar Company and a control farm between the long wet and dry seasons.30 D (125) 5.32 Site mean 5. (9053) B (8071) 7. For soils from the nucleus estate farms.63 147.1 within Nzoia nucleus estate farms.4 4.1.01 ng/mL respectively.04 C (243) 5.89 11.51 Control mean 116.28 10.17 C (243) 147.15 5.65 4. Table 4.27 5.17 81.43 8.16 5.008 ng/mL and 0.001 ng/mL. – 4.25 5.89 106.29 Control z 7. Mean Copper concentration (mg/Kg) in soils from the nucleus and from a control farm within Nzoia sugar belt Sites (in plot numbers from the nucleus and a control farm) A.22 F (429) 5.47 G (413) 9. (9053) B (8071) C (243) D (125) E (616) F (429) G (413) Site mean Control x Control y Control z Control Mean 35 . with detection limits of 0.1.31 5.08 7.38 4.60 6.62 6.63 Control x 105.161 0.54 5. the wet weight to dry weight ratio was 1.20 7.53 Control x 4.22 146.76 0.1.32 5.30 Interaction CV% Mean pH in soils from the nucleus and from a control farm within Nzoia sugar belt Sites (in plot numbers from the nucleus and a control farm) A.67 10.17 6.15 5.52 12.63 8.38 9.20 E (616) 5.59 185.335 7.31 Interaction CV% 22.81 Site mean 148. Cu.03 145.425 88.30 Control y 7.63 Control mean 4.31 Dry season Wet season Mean Lsd P≤ 0.85 161.19 7.98 134.009.20 96.4 10.24 7. Table 4.462 0.1.26 E (616) 10.66 186.03 4.27 11.95 144.53 145.015 ± 0.05 90.24 Control y 5.00 5.16 7.54 Dry season Wet season Mean Lsd P≤ 0.407 7. The AAS analysis gave mean % recovery values for extraction of the spiked soil samples of Cr.24 7.85 101.08 F (429) 10.02 G (413) 160.6 6.096 Mean Chromium concentration (mg/Kg) in soils from the nucleus and from a control farm within Nzoia sugar belt Sites (in plot numbers from the nucleus and a control farm) A.61 97.17 7.2 86.
1 2 398.38 52.52 56.08 18.41 51. (9053) Dry season 310.15 63.68 66.32 52.9 4 D (125) 424.32 63.327 Interaction CV% Mean Iron concentration (mg/Kg) in soils from the nucleus and from a control farm within Nzoia sugar belt Sites (in plot numbers from the nucleus and a control farm) A. Control xyz: Soil samples taken from a football pitch of Kanduyi primary school within Nzoia sugar belt.68 54.10 64.95 4.48 74.5 6 E (616) 533.75 56.85 130.34 71.09 70.27 93.27 160.0 5 125.99 Control z 260.30 54.3 4 182.11 Interaction CV% Mean Lead concentration (mg/Kg) in soils from the nucleus and from a control farm within Nzoia sugar belt Sites (in plot numbers from the nucleus and a control farm) A.828 6 389.61 Mean Lsd P≤ 0.13 119.05 110.2 7 G (413) 373.99 59.64 66.0 5 404.33 83.12 50.5 9 650.49 Site mean 59.984 3 368.3 2 119.49 Wet season 97.52 48.6 60.6 Control z 114.14 47.2 4 267.95 90.26 Control Mean 282. (9053) Dry season Wet season 56.673 73.05 114.0 3 Site mean 116.54 61.27 C (243) 55 49.22 Control Mean 123.62 83.53 72.0 2 154.45 69.6 57.32 53.89 Mean Lsd P≤ 0.38 115.6 5 143.57 67.02 154.08 81.7 67.964 14.7 1 161.14 73.2 8 E (616) 104.31 65.37 Control Mean 58.99 51.62 26.0 6 Site mean 410.23 122.09 13.33 84. (9053) Dry season 120.71 Control x 48.18 53.1 1 152.5 2 512.08 55.8 8.0 5 G (413) 96.1 4 B (8071) 134.05 13. 36 .01 51.69 187.4 9 263.492 9 Control x 251.5 F (429) 110.33 Control z 61.81 6.693 19.12 116.63 23.59 55.51 57.456 Interactio n CV% Key: A – G: Soil sampling points in the indicated plots on figure 3.88 124.72 F (429) 71.99 52.542 9 Control x 124.54 50.49 D (125) 63.05 9.2 7 292.36 83.67 Mean Lsd P≤ 0.9 5 120.8 67.82 224.75 70.01 Mean Lsd P≤ 0.3 4 160.96 Wet season 225.3 F (429) 684.Dry season Wet season 46.124 Interaction CV% Mean Zinc concentration (mg/Kg) in soils from the nucleus and from a control farm within Nzoia sugar belt Sites (in plot numbers from the nucleus and a control farm) A.811 4 137.38 167.66 55.8 3 B (8071) 334.55 48.4 4 D (125) 116.332 10.8 1 467.46 248.1 within Nzoia nucleus estate farms.7 1 250.0 5 264.52 75.6 3 320.6 1 225.65 Control y 336.4 5 134.7 3 576.42 84.09 36.64 G (413) 51.51 E (616) 63.29 71.05 238.45 76.0771 11.84 B (8071) 53.12 Control y 65.272 9 158.21 51.3 6 C (243) 132.363 14.8 7 414.65 Control y 131.35 75.8 6 143.4 9 C (243) 215.3 9 186.72 47.96 51.05 57.78 83.3 8 136.
Table 4.475 0. £: This study 2010 Kenya (Number of examined samples 42). a: Taiwan’s standard values to assess soil quality.471 -0.095 0.468 0. This study in comparison with international standard on heavy metals in soils (mg/kg of dry soil).250 0.530 -0.000 Table 4. c: Natural level. Heavy Metals Chromium Copper Lead Zinc Iron Key NG . d: Cleanup level.) Netherlands.584 Cr 1.000 0. Chen.667 pH 1.680 -0.693 0.3.493 -0. and Lee. (2000). b: The upper limit of the background concentration. Soil Standards€ 100*/250** 50*/500** 200*/500** 50*/150** NG Reference Values in Taiwan Soil Standards€ 100a/400b 120a/200b 50a/500b 35a/500b NG Reference Values for Dutch soil standard€ 100c/380d 36c/190d 85c/530d 140c/720d NG 37 .668 0.512 0. #: This study dry season value. ђђ: Alloway (1995a): The critical soil total concentration is the range of values above which toxicity is considered to be possible.000 0.1.473 -0. (1995). **: Reference value for good soil quality.139 0. ##: This study wet season value.237 1. €: Zuengsang.001 1. TOC% pH Cr Pb Cu Zn Fe TOC % 1.000 -0.182 0.535 Pb Cu Zn Fe 1.00 -0.Not Given in the literature.000 0. ђ: Alloway (1995a).000 -0. Control£ soil (Kenya) 142#/144## 73#/72## 59#/50## 116#/158## 409#/368## Nucleus£ soil (Kenya) 117#/108## 64#/66## 62#/51## 124#/114## 283#/167## Normal range in soilsђ 5-1500 2-250 2-300 1-900 NG Critical soil total concs. *: Tentative soil quality standards for the (Neths.ђђ 75-100 60-125 100-400 70-400 NG Reference Values in Neths.331 0.1.4.236 1. Correlation matrix of selected physicochemical parameters and heavy metals in top soils from the nucleus of Nzoia Sugar Company and a control farm between the long wet and dry seasons.
47 Ac/hectare × 50 years (USEPA 1999).676 USEPA2 standard 0.Not Given in the literature. Key NG . Risk based analysis of DAP fertilizer used in the farms of Nzoia nucleus estate for 50 years (in Kg/Ha) in comparison to international standards.000) × %Ph × Application Rate Fertilizer × 0.947 3113. 4 – Oregon standards. Risk based assessment load1 0. a: This study 2010 Kenya (Number of examined samples 150). 3 – The Association of American Plant Food Control Officials.070 1500 NG 1500 Zn 32.5.552 29. c: The soil profile 2006. 2 – USEPA 1999. 1 – This study 2010 Kenya (Number of examined samples 150).4677 2.050 57.454 kg/Ib × 2. RCRE: Rutgers Cooperative Research and Extension Table 4. 1999.1.947 2800 1850 2800 Fe 4536.1.128 0. Fe.6.6 NG 2. Cu.48 NG NG NG 5.8 NG NG AAPFCO3 standard NG NG 463 2900 NG OSDA4 standard NG NG 340 NG NG CDFA5 standard NG NG 61 420 NG Formula: Kg/Hectare = (ppm metal/1.380 247. Cr UREAa DAPa USEPAb standard Canadian c standard RCRE Suggested Limits for Sewage Sludge Key c Pb 61. Heavy metal loads in fertilizers used in the farms of Nzoia nucleus estate farms (mean ± SD mg/kg dry weight) in comparison to international standards.Table 4. 5 – California Code of Regulations section 2302 and 2303. %Ph – percent phosphate in the fertilizer.407 NG NG 1200 NG .355 0. Pb.117 300 500 300 Cu 36.170 13. Heavy Metal Cr. Ac – Accumulation. Zn. 38 .b: USEPA.Not Given in the literature.000.980 49.
2004. However the pH was significantly different between the nucleus soils and the control farm soils.05 (Tables 4.306 ± 0.. The reduction in soil pH between the two seasons was not significantly different probably due to the fact that it takes time to raise/reduce soil pH in the soil and that the slight difference in water content may not affect the pH much. This was an indication that reduction in soil pH due to use of nitrogenous fertilizers and increase in total organic carbon due to use of biosolids affected availability and solubility of heavy metals. From literature. 39 . chemical oxygen demand.8 between 1997 and 1996 (Oliver. Discussion All the studied parameters differed significantly from the control sites at P ≤ 0. Comparing the nucleus and the control soils.1 and 4.1. total organic carbon and soil pH had a nearly 50 % positive and 50% negative correlations with heavy metals respectively (Table 4. the more the solubility (Alloway.1.2). Soil pH in the nucleus soils (5. Most of the research done on acidification of sugarcane plantations with nitrogenous fertilizers has been on production line and very little work has been done to evaluate the effect of this soil pH reduction to other physicochemical parameters like heavy metals. 1995a). 1995a).0 and the lower the pH value. This was an indication that the anthropogenic activities taking place in the Nzoia nucleus (sugarcane farming) were the ones responsible for the changes in the concentration of the studied parameters. 2003).1. Woods et al.052). Apart from possible plant uptake of the heavy metals.4. the main culprit in pH change in sugarcane farming is the use of nitrogenous fertilizers. once they are soluble in the soil water. indicating the fact that the anthropogenic activity in the farms was affecting the soil pH.5 to 5.1. 2004). Reduction in soil pH has been found to be a predominant player in solubility of heavy metals (Alloway. Reduction of soil pH in sugarcane plantation has been found to be due to use of nitrogenous fertilizers which reduce soil pH during the ammonification and nitrification processes (Oliver.3). they become available for transport from one place to another especially with surface runoffs during the long wet seasons. dissolved oxygen and others. This kind of pH behavior in sugarcane plantation is typical and comparable with other areas such as Papua New Guinea recording a reduction of soil pH from 6.1.39 ± 0.31) was lower compared to soil pH from the control site (7. Most heavy metals will become soluble at pH values less than 6.
6) showed the nucleus only. 1995a).05) within the nucleus soils. which was a tree plantation that had no nitrogenous fertilizer application hence its high value of soil pH and low concentration of Heavy metals.1.2 . bear and with no fertilizer application (Table 1.) which are believed to accumulate in the soils with time. 1995).4). Generally.of history in nitrogenous fertilizer applications. the average heavy metal concentrations in both the nucleus soils and the control farm soils were above international standards (Table 4.1. though extrapolation to the whole sugar belt region may prove otherwise. There was sites variation in heavy metal concentrations (at p < 0. However Risk based analysis of the DAP fertilizer for 50 years use (Table 4. heavy metals become soluble and readily transported by surface runoffs and leaching to the aquatic environments where they accumulate in sediments and other sinks like rivers and lakes (Ongeri 2008). leaching and deposition from nearby farms may have affected the values hence use of a football pitch that was at an elevated area as the control. The nitrogenous fertilizers used in Nzoia sugarcane plantations were found to contain pollutants of these heavy metals (Tables 4. Once the soil pH has reduced to below 6. we recommend that mitigation measures be put in place to farms using nitrogenous fertilizers such that they do not affect soil pH as such for these has other repercussions like affecting bioavailability. solubility and hence mobility of heavy metals to the aquatic environments. There are no regional set standards for heavy metals in Kenyan soils hence using these international standards.1. In addition. However. factory activities may also be affecting soil pH as can be seen from plot 8071 that was adjacent to the factory.4. 40 .Most of these heavy metals are naturally occurring in the soils but they are attached to soil matrix and unavailable to plants and transport under neutral soils (Alloway. a situation that arose due to different agronomic practices at each site as is seen in Table 1. Of interest is site A (plot 9053).0. not to be contaminated with the heavy metal residues in the fertilizer used. All the same the point that nitrogenous fertilizers affect soil pH can also be seen from the fact that sampling plot A had a higher soil pH compared to other plots where fertilizers were being applied. 2008).2). However some of the heavy metals are introduced to the soil through anthropogenic activities like fertilizer application (Mortvedt. Accumulation of heavy metals in aquatic environment raises a number of healthy issues including aquatic animals like fish bioaccumulating them hence being burnt in international markets (Ongeri.
Heavy metals in water The AAS analysis gave mean% recovery values for extraction of the spiked water samples of Cr.5 below.001 ng/ml.001 ng/ml. 84. 0.2. Cu. Table 4.01 ng/ml respectively. Zn and Fe as 90. 41 .1 – 4.1. Mean site variations of heavy metal loads in surface water from canals within Nzoia nucleus estate farms (in µg/L) between the long wet and dry seasons. 79.2.2.008 ng/ml and 0. 0. The results are recorded in the Tables 4.4.003 ng/ml.a. 0. 88 and 94 respectively with detection limits of 0. Pb.2.
27 8.09 0.34 6. 3 .42 2.33 Sites 4 1.63 0.08 10.353 12. Site variations of heavy metal loads in surface water from canals within Nzoia nucleus estate farms (in µg/L) between the long wet and dry seasons.Plot 429.387 Dry Season Wet Season Mean Lsd p ≤ 0.40 4.80 5.024 6.76 Sites 4 0. Control: A canal draining water from a farm within the nucleus without sugarcane plantation (tree plantation) thus there was no nitrogenous fertilizer application.08 14.72 5. 6 .Plot 8071.09 0.82 5.724 1.46 7 3.15 3.1.07 4.00 Sites 4 1.47 5.00 0.Chromium 1(control) 0.39 19.90 1.133 Dry Season Wet Season Mean Lsd p ≤ 0.56 8.96 1.87 5.39 11.59 Mean 1.16 4.1.59 3 1.414 0.43 6 1.416 0.64 7 1.56 5 2. 42 . 2 .Plot 413 as illustrated in figure 3.44 0.94 5.26 16.58 1.2.606 13.36 3 2.80 1.55 5 1.20 1.31 1.54 0.72 7.Plot 125.52 11.05 Interaction Cv% Cupper 1(control) 2.49 3.133 1.72 5.72 9.19 6 2.697 1.68 Mean 2.35 4. 4 .81 19.59 Mean 1.22 3.40 3.78 3.59 3.60 0.93 5 0. Table 4.11 1.86 2 2.250 0.60 6.97 2.588 8.Plot 9053.Plot 616.b.34 3 2.34 2 0.46 3.66 7 0.94 2 3.492 6 3.05 Interaction Cv% Key: Canal sampling points 1 .05 Interaction Cv% Lead 1(control) 1.222 Dry Season Wet Season Mean Lsd p ≤ 0.717 2.36 0. 7 .12 2.Plot 243. 5 .
05 Interaction Cv% Key: Canal sampling points 1 .720 1.28 2 91.34 3 80.60 4.05 Interaction Cv% Iron 1(control) 101.38 162.20 123.67 107. 5 .04 206. 6 .98 169.93 132.Plot 125.487 1.498 0.01 Mean 100.49 198.161 0.000 0.19 242.37 81.2.Plot 616.92 181.94 5 114. Cr µg/L Cr µg/L Pb µg/L Cu µg/L Zn µg/L Fe µg/L 1.755 33.000 Pb µg/L Cu µg/L Zn µg/L Fe µg/L 43 .88 194.37 187.1 Control: A canal draining water from a farm within the nucleus without sugarcane plantation (tree plantation) thus there was no nitrogenous fertilizer application.000 0.18 9.13 175.00 152.32 7 33.68 7 131.62 10.738 0.77 174.28 152.455 0.44 178.14 113.79 Mean 48. 3 .18 131.Plot 243.28 2 63.38 190.000 0.19 133. 4 .63 13.92 327.000 0.59 3 46.67 Sites 4 112.674 1.Plot 9053.849 0. 2 .47 151.15 Dry Season Wet Season Mean Lsd p ≤ 0. Table 4.32 23.23 114.00 86.Plot 429.21 121.25 5 41.98 255.15 Sites 4 33.52 117.96 6 88.34 12.16 137.2.03 133.70 Dry Season Wet Season Mean Lsd p ≤ 0.Plot 413 as illustrated in figure 3. Correlation matrix of heavy metal loads in water samples from canals within Nzoia Sugar Company nucleus estate farms.64 5.129 1.33 6 69.153 0.77 114.Plot 8071.Zinc 1(control) 31. 7 .57 127.
44 3.3.268 6.56 2.538 0.140 Sites 2 2.560 3 2.84 3.95 0.783 4.403 0.513 0.Table 4.067 0.570 3.177 0.515 Sites 2 0.05 Interaction Cv% 0.41 3.50 0.573 4.53 8.162 Sites 2 1.054 Lead Dry season Wet season Mean Lsd p ≤ 0.207 0.62 4. 44 . 2 – A point in the river at the middle of the Nzoia nucleus sugarcane farms.05 Interaction Cv% 1(control) 1. 3 – Outlet of River Kuywa from Nzoia nucleus estate farms (subtract from the control to get the impact of the nucleus).41 4.421 0.094 6.698 0.352 0.670 Mean 1.90 5.51 3 1.a.70 3.586 0.761 16. Site variations of heavy metal loads in surface water from River Kuywa within Nzoia nucleus estate farms (in µg/L) between the long wet and dry seasons.68 0.87 4.360 Copper 1(control) Dry season Wet season Mean Lsd p ≤ 0.89 5.728 Mean 0.05 Interaction Cv% 1.40 6.629 27.718 Mean 2.820 0.2. Chromium 1(control) Dry season Wet season Mean Lsd p ≤ 0.819 0.220 3 0.440 Key 1 – Inlet of River Kuywa to the Nzoia nucleus sugarcane estate farms (used as a control so as to give the impact of the nucleus).445 0.35 0.
31 65.352 6.844 3. 45 .16 Mean 23.87 7. Zinc Sites Dry season Wet season Mean Lsd p ≤ 0.05 Interaction Cv% 1(control) 17.553 Iron Dry season Wet season Mean Lsd p ≤ 0.53 2 26.20 41.18 47.49 45.72 79.05 Interaction Cv% 1(control) 66.942 118.809 40.37 Mean 81.365 10.740 3 28.880 57.30 108.170 3 97. 3 – Outlet of River Kuywa from Nzoia nucleus estate farms (subtract from the control to get the impact of the nucleus.85 4.72 92.009 Key 1 – Inlet of River Kuywa to the Nzoia nucleus sugarcane estate farms (used as a control so as to give the impact of the nucleus).72 Sites 2 81.3.Table 4.94 126.697 100.13 66. 2 – A point in the river at the middle of the Nzoia nucleus sugarcane farms.80 154.320 6.42 94. Site variations of heavy metal loads in surface water from River Kuywa within Nzoia nucleus estate farms (in µg/L) between the long wet and dry seasons.2.155 5.410 5.b.85 29.
000 Pb µg/L Cu µg/L Zn µg/L Fe µg/L Table 4.887 0.2.000 0.5.781 1.000 0.2.770 1.000 0.000 0.902 0.904 0. Cr µg/L Cr µg/L Pb µg/L Cu µg/L Zn µg/L Fe µg/L 1.4.911 0.989 0. Correlation matrix of trace metal loads in water samples from River Kuywa.794 1.Table 4.911 0. 46 . Comparing with some international standards on domestic water and data from other studies for heavy metals.793 1.
81 5000 5000 120 120 200 500 2000 >2000 150-4100 0. h – Pettine et al. Class i – Clean water for domestic use.84 50 50 10 50 15 100 53.405 Cu µg/L 2. Guidelinee: Class i Class ii Class iii Class iv d c a a a Pb µg/L 1.025 2.94 100.5 522.95 57.6 3.491 198.8 4.16 81.697 0.6 14.2 1. m – Ongeri (2008).2-138.8 10-110 5 NG 5 5 5 3 14. Class iv – Heavily polluted water.219 1.00 10 NG Key NG – Not Given in literature. j – USEPA (1980). (2000).15 2-66 1-17 NG NG NG Dil Deresi Streamf Indian River Florida Lambro River Italy USEPAj UK EU k k k h i g Gediz River Turkry Canada USAk Russia k NG NG NG m Winam gulf NG NG NG NG NG NG NG 0.051 Fe µg/L 100. k – Neubauer and Wolf (2004). n – Ahmet et al. (2004).9 253. Discussion 47 .50 47.606 13.2 1.Cr µg/L This studya dry season canals This study wet season canals This study dry season Kuywa This study wet season Kuywa KEBSb Standard WHO standard Waterquality criteria CMC CCC Turkish env.4 4. (2005).5 132.3 300 300 NG NG NG NG NG NG NG NG NG NG 300 200 200 300 300 300 2778 216. d – USEPA (1999).049 2835 2320 NG 1.1.8 20. (1996).1 232.338 50 10 65 25 10 20 50 >50 11-370 0.90 48.1 1.00 44. a – This study 2010 Kenya (number of examined samples: 18 for river and 42 for canals) b – KEBS (1996). l – Klavins et al.352 0.240 100 1000 13 9 20 50 200 >200 11-94 1. Victoria basin) Municipal water (L.268 6.365 Zn µg/L 48.2.092 l Rain water (L. e – Turkish Environmental guidelines (1988).819 NG NG 16 11 20 50 200 >200 16-110 0.564 2. Class iii – Polluted water.00 0.60 47. i – Bakaa and Kumru (2001).870 5. Class ii – Fairly clean water for domestic use.7 52. f – Perkey et al.5 267. Victoria basin) Well waterm (L. World average 4.2 NG 13. g – Trocine and Trefry (1996).760 6.40 57.8 NG 3-46 5000 5000 100-5000 5000 5000 5000 237 228.13 175. Background Conc.5 213.4 0.1-134.20 23.4 18.3 225. Victoria basin) m m Nyamasaria river Nyando river Dipsiz river n m m Sondu mirio riverm NG 0.131 1. c – WHO (1998).
The increase in the concentrations during the long wet season was attributed to surface runoffs that acted as transport agent of the heavy metals from the farms to the aquatic environment.2. Heavy metals (Cr. Cr. Zn and Fe) concentrations in water samples differed greatly from the control site in the canals (Table 4. Furthermore. Nyando and Winam Gulf have higher heavy metal concentrations (Ongeri.2. The same results can also be supported by the fact that the heavy metals correlated with each other positively further indicating their common origin (Tables 4. Continuous accumulation of heavy metals and soil pH reduction may make the values to increase. Cu. From the results the nucleus estate farms that are a total of 4000 ha contributed positively to the total heavy metal (Cu.2.5). 2008. the pH of the soils was way below 6. Extrapolating the results to out growers (approximately 16500 ha) makes the contribution enormous.3a&b).2.5) as compared to River Kuywa partly because of the distance traversed by these rivers as compared to the short Distance traveled by River Kuywa.5 indicates that the values of heavy metals in water are within limits. though there is need for monitoring the values for a longer period of time to validate this claim.4).2.0 a value at which the heavy metals start being soluble hence easily transported to the aquatic environment. water samples fall under class (i) of domestic water indicating the water to be within allowable limits with heavy metal concentrations (Table 4. Nzoia sugar plantations were used to find the effect that arises due to use of nitrogenous fertilizers in sugarcane plantation which is a major cash crop in Bungoma.3 a&b).2. Although Table 4.2. soil erosion and leaching also aid in heavy metal transport from the sugarcane plantations to the aquatic environments hence there increased concentrations in water samples during the wet season. Other Rivers like Sondu Mirio. Zn. Nyamasaria. Table 4. All the same. Lugari and Kakamega Districts from Western Kenya.2 and 4.2.1 a&b) and the nucleus contribution to River Kuywa was statistically significant at P ≤ 0. considering the impact on out growers in the three Districts as a whole and relating the concentrations to River Nzoia that traverses the Districts may make the concentrations found to be of considerable concern. 1995a) and as already discussed.05 (Table 4. According to Turkish environmental guidelines (1988).The amount of heavy metals in a water system is subject to local and international standards and regulations due to the health effects they pose to human beings in the higher food chain and the aquatic animals in the lower food chains. Pb. the contribution 48 . This was probably due to the fact that the solubility of all the studied heavy metals increase with reduction in pH (Alloway. Pb and Fe) burden in River Kuywa (Table 4.
River Kuywa drains its water into River Nzoia that finally drains into Lake Victoria. Heavy metals in Sediments 49 .3. Heavy metals in River Nzoia are already above international standards (Lalah et al. probably due to the fact that the river basin of River Nzoia comprises mostly of sugarcane plantations. 2008).of the nucleus to heavy metal burden into River Kuywa is significant making sugarcane farming a major contributor of Heavy metals to the water system. 4.. There is therefore need to monitor soil pH which is a major factor in heavy metal mobility from the farms so as to avoid there accumulation into aquatic environments.
001 ng/ml.18 Key: Canal sampling points 1 .87 3.20 84.14 25.04 56.001 ng/ml.Plot 8071.008 ng/ml and 0.66 86.Plot 125.06 9.58 40.42 51. 5 .b.89 50.63 94.a.15 3 51.3.93 52.04 50.019 g giving an average of wet weight to dry weight ratio as 1.43 Mean 5 15. 94.67 45.70 55. Table 4. respectively. Control: A canal draining water from a farm within the nucleus without sugarcane plantation (Tree plantation) thus there was no nitrogenous fertilizer application. 0.19 7 14.Plot 9053.421 11. 3 .97 8. 2 .13 38.17 5.1.72 3.58 2 34.42 36.46 38.Plot 429.57 3 31.53 52.10 50.41 40.968 ± 0.80 74.77 Cupper Dry Season Wet Season Mean Lsd p ≤ 0.19 7 24.45 37.22 60.61 106. Zn and Fe as 93.05 Interaction Cv% 1(control) 19. 6 .1.036 ± 0.02 61.75 18.Plot 413 as illustrated in figure 3.67 51.14 42. 88 and 84.38 43.82 56.16 3.80 Sites 4 29.26 19. Pb.05 Interaction Cv% 1(control) 14.Plot 616.81 52. 50 .12 20.96 8.42 38.01 Mean 5 30. Table 4.69 81. Cu.26 74.30 73.40 7 26. The wet weight for sediments was 1g per sample while the dry weight averaged to 0.16 39.66 26. 89.71 6 33.62 Sites 4 51.1.024.3.05 Interaction Cv% 1(control) 31.20 51. with detection limits of 0.Plot 243.53 63. 7 .003 ng/ml.77 Lead Dry Season Wet Season Mean Lsd p ≤ 0. 0.73 5.74 Sites 4 25. Mean site variations of heavy metal loads in surface sediments from canals within Nzoia nucleus estate farms in mg/kg between the long wet and dry seasons.65 49.01 ng/ml respectively.78 56.98 13.27 58.44 7. 4 .18 Mean 5 59.79 39. Chromium Dry Season Wet Season Mean Lsd p ≤ 0.506 39.91 7.53 78.42 2 64.19 6 48.16 6 18.95 56.87 54.46 43. Mean site variations of heavy metal loads in surface sediments from canals within Nzoia nucleus estate farms in mg/kg between the long wet and dry seasons.58 17.12 2 23.44 3 25.52 72.The AAS analysis gave mean % recovery values for extraction of the spiked sediments samples of Cr. 0.44 54.
05 Interaction Cv% 147.47 2.51 94.99 103.75 360.33 6 62.Plot 125.22 212.97 242.71 155.426 0.3.675 0.35 439.000 0.93 12.16 7 211. Correlation matrix of heavy metal loads (mg/kg of dry weight) in sediments samples from canals within Nzoia Sugar Company nucleus estate farms.06 3 84.76 324.a.31 213.473 0.713 Cu 1.88 87.58 7 128.Zinc Sites 1(control) Dry Season Wet Season Mean Lsd p ≤ 0.23 71.173 Zn Fe 1. 6 .79 312. Table 4.48 91.Plot 429.3.68 273.76 2 111. 2 .Plot 413 as illustrated in figure 3. 5 .1.Plot 616.72 6 255. 3 .000 0.19 327.260 8.3.66 5 215.73 4.92 187.Plot 9053.01 112.610 5 110.09 85. Control: A canal draining water from a farm within the nucleus without sugarcane plantation (Tree plantation) thus there was no nitrogenous fertilizer application. 4 .30 8. Cr Pb Cu Zn Fe Cr 1.82 12.207 0. Mean site variations of heavy metal loads in surface sediments from River Kuywa within Nzoia nucleus estate farms in mg/kg between the long wet and dry seasons.28 178.Plot 8071.53 216.30 182.207 17.000 -0.39 105.2.068 0. 7 .53 113.53 Mean Iron Sites 1(control) Dry Season Wet Season Mean Lsd p ≤ 0.99 4 86.80 6.52 203.82 112.05 Interaction Cv% 98.360 0.71 4 184.71 Mean Key: Canal sampling points 1 .000 Table 4.50 297.Plot 243.09 222.67 95.78 103.60 133.328 Pb 1.000 0.55 290.20 2 92.23 210.38 97. 51 .01 3 186.082 1.92 80.
Chromium Sites 1(control) Dry season Wet season Mean Lsd p ≤ 0.45 59.19 50.78 53.89 Mean 36.47 57.190 6.b.3.3.91 67.59 53.66 Mean 39. 2 – A point in the river at the middle of the Nzoia nucleus sugarcane farms.76 2 46.77 72.75 52.53 Copper Sites 1(control) Dry season Wet season Mean Lsd p ≤ 0.22 65.83 49.59 3 44.72 83.55 6.27 66.51 6.20 5.650 3 45.40 56.34 39.84 9.91 47. 3 – Outlet of River Kuywa from Nzoia nucleus estate farms (subtract from the control to get the impact of the nucleus). Table 4.82 66.05 Interaction Cv% 28.67 16.08 Mean 41.62 50.92 54.38 56.05 Interaction Cv% 29.51 11.33 69.497 9.07 2 37.78 63.05 63.30 Key 1 – Inlet of River Kuywa to the Nzoia nucleus sugarcane estate farms (used as a control so as to give the impact of the nucleus).27 65.76 53. 52 .56 11.05 Interaction Cv% 35.65 3. Mean site variations of heavy metal loads in surface sediments from River Kuywa within Nzoia nucleus estate farms in mg/kg between the long wet and dry seasons.44 4.11 4.72 Lead Sites 1(control) Dry season Wet season Mean Lsd p ≤ 0.99 3 48.44 2 38.
Correlation matrix of heavy metal loads (mg/kg of dry weight) in sediments from River Kuywa.23 122.700 1.5.33 13.919 0.05 3 129.00 Mean 122.760 0. 2 – A point in the river at the middle of the Nzoia nucleus sugarcane farms.107 2 384.90 376.17 14.86 113.000 0. Comparing with some studies done on sediments from other rivers 53 .57 399.05 Interaction Cv% 1(control) 104.58 1.16 133.85 3 420.98 17.3.870 1.09 Iron Sites 1(control) Dry season Wet season Mean Lsd p ≤ 0.621 0.54 Sites 2 132.55 139.93 162.19 Mean 386.000 Pb Cu Zn Fe Table 4.31 Key 1 – Inlet of River Kuywa to the Nzoia nucleus sugarcane estate farms (used as a control so as to give the impact of the nucleus).05 Interaction Cv% 353.06 146.806 1. Table 4.42 147.4.821 0.64 444.000 0.54 11.31 398.000 0.000 0.873 0.09 414.3.26 24.19 144.41 7.73 467.04 406.810 1.Zinc Dry season Wet season Mean Lsd p ≤ 0. Cr Cr Pb Cu Zn Fe 1. 3 – Outlet of River Kuywa from Nzoia nucleus estate farms (subtract from the control to get the impact of the nucleus).867 0.85 19.04 427.
00 20. b – Ongeri (2008).30 137 ± 5 140 ± 3 10.40 418.10 25.80 172.57 41.42 39.90 28.36 67.2 37. (2005).00 13.05 459.00 197.30 56.2 144. h – Charle (2002). (1998).82 112.00 25.1 427. h – Background concentrations (Bervoets and Blust.00 94.00 370 28.53 79.60 651.10 25. 54 . e . (2002).00 54.00 19. (1999).00 14.60 NG NG NG NG NG NG NG NG NG – Not Given in literature.20 120 ± 10 160 ± 15 64. d – Ahmet et al.700 NG 17..40 131.59 18.81 17. a – This study 2010 Kenya (number of examined samples: 18 for river and 42 for canals).81 66.75 72. 2000).50 20.92 8.47 57.00 128 ± 15 21. g – PEC: Probable effect concentrations (Mac Donald et al.00 26.93 52.RIVER Cr mg/kg Pb mg/kg Cu mg/kg Zn mg/kg Fe mg/kg This studya dry season canals This studya wet season canals This studya dry season R. c – Akcay et al.0 298. f – Kidd et al.Kuywa This studya wet season R.60 158. 2003).70 NG 111.30 685.1 9.70 0.0 386.51 36.10 17.89 50.Kuywa Sio River Kenyab Sondu Mirio River Kenyab Nyamasaria River Kenyab Nyando River Kenyab Buyuk Menderes River Turkeyc Gediz River Turkeyc Lake Boeuf Lousianae Lake Malawif PECg Dipsiz Streamd Lake Tanganyikai Back ground concentrationsh 43.Aucoin et al.8 122.30 111.60 14.00 83.00 14.90 37.83 NG NG NG NG 165 ± 7 200 ± 6 11.70 258.
sediments have been widely used as environmental indicators and their chemical analysis can provide significant information on the assessment of anthropogenic activities (Shriadah. Fabbri et al.3 a&b) in the river and canals sediments that increased downstream River Kuywa was an indication of pollution loading due to sugarcane farming and nitrogenous fertilizer application in the nucleus estate farms. 1998. As indicated earlier.3.3. heavy metal loads correlated with each other positively further indicating their common source (Tables 4. Valdés et al....3. Cu. The heavy metals studied (Cr.... the main factor in the mobility and subsequent accumulation of heavy metals in the river sediments is the reduced soil pH due to use of nitrogenous fertilizers. 4. Kamau. 2005... In canals and river sediments. 1999. Badran and Zibdah.2 and 4. 2002. Sio. Ranjbar. In the current study therefore. 2005. sediments form an important repository of heavy metals (Ravanelli et al.1. Furthermore. and Fe) were above background values (Chale. the values increased drastically during the wet season probably due to surface runoffs in the sugar plantations (Figure 4. 4. 2000. Zn.4). Veen et al. and the heavy metal pollution of aquatic ecosystems is often most obviously reflected in high metal levels in sediments. Table 4.3. in water bodies. 2003. Thus. Mathew et al.) Heavy metal loads in the nucleus sediments (both river and canals) were above other studied Rivers like Nyamasaria. Nyando and Sondu Mirio within Lake Victoria basin (Ongeri.. 2005). the high concentration of heavy metals (Tables 4. 2006. Singh et al. Discussion In a river system. Nemr et al.3.5).1a&b. Sekhar et al.3. 2008).3. 2005). 2001. Panda et al. 55 .3. 2006.4. Jain et al. Though this can be attributed to the fact that this was a point source and the reported values are assumed to be the average for the entire river... 2001. other than in elevated concentrations in underlying water (Linnik and Zubenko. 2003. 2006).1.3. Gaur et al. 2002. 1997. Pb.
91 7 8.60 256.Plot 243. 3 .92 5.22 565.33 3.00 6 24.00 22.00 3 28.17 2 73.29 5 6.21 4.062 0.83 6 52.70 260.83 7 33.35 4.33 412.Plot 9053.86 5.05 Interactions CV% 1(control) 88.67 149.00 120.Plot 125.63 379. 7 .63 9.53 6.13 Mean 6.33 0.48 2 6.05 Interactions CV% 1(control) 3.00 20.12 4.4.00 26.37 697.90 346.1.27 24.04 3.92 3.86 5.88 Sites 4 6. 6 .00 198.07 3 7.Plot 429.00 Sites 4 25.00 631.61 5.05 Interactions CV% 1(control) 105.4.33 811.14 4. 2 .00 23.11 Sites 4 224.92 5.03 2.14 3 5.80 5.088 3. 4 .00 21.25 0.36 3.17 2 116.11 4.05 Interactions CV% 1(control) 27.67 317.70 504.00 0.867 207.84 2.00 24.030 Sites 4 6.67 202.134 Turbidity (NTU) Dry season Wet season Mean Lsd p ≤ 0.00 Mean 26.53 6.00 7 31.33 167.12 4.63 2 4. Control: A canal draining water from a farm within the nucleus without sugarcane plantation (Tree plantation) thus there was no nitrogenous fertilizer application.00 Mean 4.33 353.033 Key: Canal sampling points 1 .00 24.4.33 308.73 6.23 4.43 23.02 Sites 3 4 42.00 5 5.20 5.33 158. Table 4.4.62 6 3.52 5.43 Mean 57.00 26.50 54.94 7 5.Plot 616.00 25.951 4.79 Conductivity (µS/cm) 5 60.30 6 7. Mean site variation of some water quality physicochemical parameters in canals inside the nucleus estate farms of Nzoia Sugar Company between the long wet and dry seasons.42 106.49 Mean 94.78 3.08 4.3400 pH Dry season Wet season Mean Lsd p ≤ 0. Physicochemical parameters in water Table 4.76 4.376 0.67 533.00 27.41 674.50 3 69.91 5.00 353.98 Dissolved Oxygen (mg/L) Dry season Wet season Mean Lsd p ≤ 0.920 3.50 2 26.95 246.45 5 61.68 183.136 Dry season Wet season Mean Lsd p ≤ 0.67 708.00 121.71 152.01 4.15 31.13 4.37 16.13 6.340 8.51 697.32 0.77 44.00 25.05 Interactions CV% 1(control) 6.28 956.1.93 0.86 0.00 26.00 22. Mean site variation of some water quality physicochemical parameters in Temperature (oC) Dry season Wet season Mean Lsd p ≤ 0.45 6 32.04 5.050 5 24.Plot 413 as illustrated in figure 3.00 458.235 0.40 5. 56 .166 0.00 25.37 7 52.975 4.Plot 8071.2. 5 .
000 pH Cond µS/cm Turb NTU DO mg/L COD mg/L TP mg/L NO3-N mg/L Table 4.929 1.731 -0.763 0.831 0.130 -0.899 0.861 0.563 0.356 0.906 1.539 0.978 0.624 1.631 -0.844 0.360 0.3.583 -0.456 -0.4.621 -0.000 -0.753 0.812 -0.819 Cu µg/L -0. Cr µg/L Temp pH Cond Turb DO COD TP NO3-N -0. Correlation matrix of physicochemical parameters of water samples from canals within Nzoia nucleus estate farms.552 0. Temp o C Temp pH Cond µS/cm Turb NTU DO mg/L COD mg/L TP mg/L NO3-N mg/L 1.834 -0.713 0.000 0.695 -0.648 Zn µg/L -0.530 0.843 1.828 0.794 0.764 -0.716 0.358 -0.830 0.879 -0.643 -0.576 -0.424 -0.189 0.342 Pb µg/L -0.839 0.903 1.596 -0.681 0.550 -0.4.Table 4.746 0.000 -0.000 0.390 0.885 0.751 0.000 0. Correlation matrix of heavy metal loads and physicochemical parameters in water samples from canals in Nzoia nucleus estate farms.532 -0.868 0.692 0.368 0.000 -0.802 -0.789 0.757 0.481 1.4.000 0.800 -0.867 Fe µg/L -0.840 0.785 0.691 0.872 -0.759 -0.817 1.687 57 .600 0.
Temperature oC Sites Dry season Wet season Mean Lsd p ≤ 0.43 106.58 0.136 Conductivity (µS/cm) Sites Dry season Wet season Mean Lsd p ≤ 0.05 Interactions CV% 1(control) 42.97 3 65.80 6.428 Turbidity (NTU) Sites Dry season Wet season Mean Lsd p ≤ 0.21 968.00 Mean 25.4.97 2 52.Table 4.17 22.52 14.50 23.740 3.72 2 62.22 6.54 3 6.523 0.00 22. 3 – Outlet of River Kuywa from Nzoia nucleus estate farms (subtract from the control to get the impact of the nucleus).52 24.59 Mean 62.00 2 25.83 515.00 79.36 966.307 Key 1 – Inlet of River Kuywa to the Nzoia nucleus sugarcane estate farms (used as a control so as to give the impact of the nucleus). Mean site variation of some water quality physicochemical parameters from River Kuywa inside the nucleus estate farms of Nzoia Sugar Company between the long wet and dry seasons.22 21. 2 – A point in the river at the middle of the Nzoia nucleus sugarcane farms.166 0.33 88.30 6.00 23.00 24.03 6.44 3 61.17 514.56 5.27 6.48 Mean 52.40 9.64 524.783 Sites 2 7.54 983.06 4.23 pH Dry season Wet season Mean Lsd p ≤ 0. 58 .05 Interactions CV% 1(control) 7.50 21.090 6.50 3 26.05 Interactions CV% 1(control) 58.584 0.70 507.16 6.83 23.078 6.22 104.370 Mean 7.89 78.235 0.60 93.781 0.53 0.598 0.73 956.33 67.05 Interactions CV% 1(control) 24.5.27 17.63 115.94 5.
45 20. Dissolved Oxygen (mg/L) Sites Dry season Wet season Mean Lsd p ≤ 0.44 4.612 8.703 8.655 6.40 12.878 1. Mean site variation of some water quality physicochemical parameters from River Kuywa inside the nucleus estate farms of Nzoia Sugar Company between the long wet and dry seasons.213 Chemical Oxygen Demand (mg/L) Sites Dry season Wet season Mean Lsd p ≤ 0.05 Interactions CV% 1(control) 14.67 1710.05 Interactions CV% 1(control) 0.401 0.83 2 1303.40 10.133 Mean 11.25 17.902 Total Phosphates (mg/L) Sites Dry season Wet season Mean Lsd p ≤ 0.938 115.997 0.148 11.369 12.76 8.84 1.05 Interactions CV% 1(control) 1213.64 3 14.261 0.758 10.143 1.33 1656.05 5.00 81.05 Interactions CV% 1(control) 1.042 4.33 1398.23 8. 59 .148 6.33 1598.18 Mean 2.450 Key 1 – Inlet of River Kuywa to the Nzoia nucleus sugarcane estate farms (used as a control so as to give the impact of the nucleus).50 Mean 1334.717 12.54 2 1.616 0.933 Total Nitrate Nitrogen (mg/L) Sites Dry season Wet season Mean Lsd p ≤ 0.4.39 10.86.99 9.26 9.44 66.44 1650. 3 – Outlet of River Kuywa from Nzoia nucleus estate farms (subtract from the control to get the impact of the nucleus).33 1584. 2 – A point in the river at the middle of the Nzoia nucleus sugarcane farms.68 1480.82 8.40 2 10.450 14.381 9.82 Mean 1.327 17.93 7.00 2 2.28 14.90 3 9.46 0.51 6.62 3 3.40 3 1.6.853 10.26 4.Table 4.44 1492.
811 -0.656 -0.843 -0.764 0.923 0.524 0.914 -0.478 0.547 -0.896 -0.4.898 Zn -0. Cr Temp 0C pH Cond µS/cm Turb NTU DO mg/L COD mg/L TP mg/L NO3-N mg/L -0. Correlation matrix of physicochemical parameters of water samples from River Kuywa.630 0.476 0.732 -0.952 0.797 0.427 -0.962 -0.895 0.7.547 -0.764 0.134 0.950 0.433 0.000 -0.847 0.000 -0.695 -0.472 0.916 0.083 -0.972 1.000 0.747 -0.772 0.796 -0.797 -0.324 -0.000 pH Cond Turb DO COD TP NO3-N Table 4.711 -0.623 0.942 Pb -0.991 0.833 -0.276 0.775 -0.819 0.000 -0.942 Fe -0.814 -0.957 Cu -0.824 1.775 -0. Correlation matrix of heavy metal loads (µg/L) and physicochemical parameters in water samples from River Kuywa.981 1.731 60 .682 -0. Temp Temp pH Cond Turb DO COD TP NO3-N 1.726 0.000 0.000 -0.949 0.976 1.602 -0.515 -0.8.297 1.862 -0.908 -0.634 1.899 1.341 0.951 0.955 0.Table 4.931 0.941 0.4.018 -0.370 0.000 -0.
Table 4.4 4.770 405.9.22 59.5-8.30 129.667oC and 21. There is no set standard for temperature on drinking or domestic water.00 170.00 410.222 ± 0.100 2.85 5.40 10.00 945. a – This study 2010 Kenya (number of examined samples: 42 for canals and 18 for river water).).00 202.5 7.6 104.326 21.949 3.9 94.149 2.42 6. Comparing with some international standards on domestic water and levels of metals reported in other studies for physicochemical parameters. 4.00 4.15 25.5).5-8.96 57.50oC and 26.83 NG NG NG NG NG NG NG 28.975 808.00 26.5-8.00 230.000 NG NG NG NG 190.090 52.61 1197.028oC during the dry and wet seasons respectively (Table 4.8 NG NG NG NG NG 145. f – ECS (Egyptian chemical standards) (1994) permissible limits. d – USEPA (1979) permissible limits.76 NG NG 0.7 5.8 7.5 6 . 00 28.61 11.5 6.95 23.20 NG 10. maybe due to the 61 . Kuywa KEBSb Standard WHOc standard USEPAd standard EMCA(WQ)g2006 std Egyptian standardf Winam Gulfe Lake Victoriae Sio Rivere Nyamasaria Rivere Nyando Rivere Sondu mirio Rivere 26. c – WHO (1993) maximum permissible limits.08 4.1.00 28.000 10.00 980.8 7.000 143.833 ± 0. while for River water it ranged between 24.7 8.00 6.356 6. e – Ongeri (2008) downstream for rivers. Temp 0 pH Cond µS/cm Turb NTU DO mg/L COD mg/L TP mg/L NO3-N mg/L C This studya dry season canals This studya wet season canals This studya dry season R.65 1226.250oC during the dry and wet seasons.90 246.0 NG NG NG NG NG NG NG NG NG NG NG 12.00oC with a mean of 25.381 NG NG 4–5 NG 10.9.7 697.4.000 NG NG NG NG NG NG NG 44.4.80 76.5 6–9 7.5 0.20 4. Kuywa This studya wet season R.37 33.429 ± 2.0 3.4.48 5.3 7.4.378°C and 23.000 NG NG NG NG NG NG NG NG Key NG – Not Given in literature.16 7.5 7.28 4.1 Discussion Canal water temperature ranged between 20°C to 31°C with a mean of 26.00 8.0 1.668 25. respectively (Table 4. g – Kenyan EMCA (WQ) (2006) Standards.96 7.286 ± 0.5 6. b – KEBS (1996) maximum permissible limits.
1 and 4.4. The variations in conductivity were statistically significant from the control site. Lake Victoria and Sio in Lake Victoria basin (Ongeri 2008) Canal turbidity site mean ranged from 32.4.779 µS/cm dry and 104.). Increased conductivity means that heavy metals become bioavailable hence readily absorbed by aquatic plants and animals in essence affecting the food chains (Wang.188 NTU in both seasons with seasonal means of 62.618 NTU for wet season (Table 4. between seasons and even in interactions (Table 4.867 ± 5. Ongley. Canals Electrical Conductivity ranged from 33. Nyamasaria.4.667 ± 5. Driscoll et al.1) while.407 ± 1.3.05 Table 4.4.779 NTU for dry season and 968.4.430 NTU to 983.33 ± 4.5.410 ± 141.).163 µS/cm with means of 62. This was an indication of surface runoffs and erosion in the farms contributing positively to the above mentioned physicochemical parameters.4.315 NTU in both seasons with seasonal means of 94. an indication of runoffs from the fields during the rainy season.112 NTU to 956.4.05 (Table 62 . There was drastic increase in turbidity during the wet season (Figures 4.) and the alternative hypothesis adopted.824 NTU for dry season and 697. Gough and Herring.252 µS/cm wet seasons (Table 4.4. Conductivity increased drastically during the wet season with the distribution showing positive skewness.).). and 4.05).740 µS/cm to 115. 1987.119 NTU for wet season (Tables 4.4.5). 1993.5).63 ± 5. The null hypotheses for temperature were not rejected at all levels (P ≤ 0. river turbidity site mean ranged from 58. Site and seasonal variations were also statistically significant from the control site (Tables 4.426 µS/cm to 353.714 ± 65.4.212 ± 3.3. and 4. All the null hypotheses were rejected for conductivity at all the significant levels (P ≤ 0.1. Conductivity levels in the wet season was above other studied Rivers like Sondu Mirio.600 ± 2.722 µS/cm dry and 246. 1994.1.4. That notwithstanding the observed differences in temperature per site remains to be out of contingency and that of seasons does not depend on sugarcane farming in Nzoia nucleus estate farms but maybe out of other factors not studied.700 ± 3.5.1. Turbidity correlated with most of the other physicochemical parameters for it had nearly perfect positive linear correlations with chemical oxygen demand.957 ± 17.733 ± 1. total phosphates.88 ± 0.4.83 ± 13. for example time of the day during sampling.508 µS/cm with means of 57.967 µS/cm wet seasons (Table 4. 4.7)..4. while that of River Kuywa ranged from 42. 4. Increase in conductivity is an indication of increased loads of metallic ions in the water during the wet season.212 ± 3. Generally the null hypothesis was rejected significant level P ≤ 0.480 ± 61. and NO3-N (Table 4.fact that there is no scientific evidence on effect of temperature in drinking water.1.4. 1996).5.
5). 2008).905 ± 0.170 dry season and 6. Ford et al. Surface water runoffs into the river and the canals could be the one responsible for the low pH values in the wet seasons.8) an indication that the heavy metal loads in water samples were directly linked to surface runoffs and erosions in the sugarcane plantation fields. 1996). KEBS.5 (WHO.770 ± 0. This observed difference is due to reoxidation of the high metal concentrations during the wet season (Table 4. EMCA.309 wet season (Table 4.5 . For river water. turbidity correlated positively with heavy metals (Tables 4. Water from canals and River Kuywa within Nzoia nucleus estate farms should not be used for domestic purposes in the wet season because its pH is not within the permissible limits of 6. Turbidity levels in the water within the canals and River Kuywa were above international standards hence it was not suitable for domestic use as residents downstream River Kuywa.4. the mean values were 7. 1995b.4 and 4. and Nyamasaria (Ongeri. From these correlations we clearly observe that an increase in NO3-N results in reduction in pH values as it had earlier on been reported by Dobermann and Fairhurst (2000). 1993. and NO3-N.1 and 4.1 and 220.127.116.115 for dry season and 4. The pH site values in water ranged between 8. 1994). (KEBS.18.104.22.168 (USEPA.381 ± 2.130 ± 0.4.968 ± 0.1 and 4.397 mg/L river water) as compared to the wet season (mean of 3..133 ± 0. (Table 4.1).09 ± 0. The pH value for the river during the wet season was below other rivers like River Sio.. The turbidity levels compared to that of River Nyando that had been reported to have a value of 980 NTU. Hence this makes dissolved oxygen reduce with increase in dissolved metals. pH gave a very strong negative linear correlations with conductivity. Chemical Oxygen Demand. 1996.975 ± 0. 2001).4. Reduced water pH accelerates solubility of heavy metals from the sediments into water making them bioavailable hence bioaccumulating into aquatic animals and (Alloway. Nyando.5). 1982).010 to 4.4. 2006). Total Phosphates.3). 6 – 9.4.612 ± 2.3) as compared to the dry season where the concentration of the metals is low (Table 4.2. The net effect is that a high concentration 63 .019 mg/L river water ). Thus an increase in dissolved oxygen also increases dissolved metals hence promoting mobilization (Duinker et al.4. This could be so due to the fact that the nitrogenous fertilizers have affected the soil pH in the farms and hence the same is replicated in the water system.3 and 4.682 for wet season in canals water (Table 4.954mg/L canal and 11.356 ± 0. In addition.2. 1979) and 6 – 9 (Egyptian Chemical Standards.7).4. Dissolved oxygen was high during dry season (mean of 4.964 mg/L canal and 8.208 in both seasons with seasonal means of 6.
1226.538 mg/L wet season. Except for the dry season samples.05) (Tables 4.903) canal water (Table 4.1. Pb: -0. Zn: -0. Generally rain water runoffs in the farms carry with them contaminants like phosphates and nitrates that increase biological activities in the canals water hence increasing COD levels.5) hence the adoption of the alternative hypotheses. Chemical Oxygen Demand increased rapidly during the wet season with means of 405.4 (Cr: -0. Table 4. concentration of 64 .324 river water).530 canals) and Tables 4. values which were above USEPA (1979) and EMCA (2006) standards especially in season two (Table 4.586 mg/L) (Figures 4.1 ).827 ± 110. Total phosphates had a nearly perfect positive linear correlation with conductivity (0.4. turbidity (0.861).4.2 and 4.4.4. Tables 4.5).4. There were very little phosphates in the canals water during the dry season (mean: 0.767 ± 4.751. Fe: -0.903).682.241 mg/L dry season and 808. Pb: -0. turbidity (0.692.149 ± 0. The same observation is seen in River Kuywa with concentrations of 1.3). Since second season sampling was done just two weeks after nitrogenous fertilizers had been applied in the farms.1 and 4.668 ± 2.4.949 ± 0.828) (Table 4.8 (Cr: -0. NO3-N (0.251 mg/L dry season and 12.4.1) and 1197. All the null hypotheses were rejected at all significant levels (P ≤ 0.630.4.4. and COD (0.7).002 mg/L dry season.5).4. Cu: -0.335 mg/L) but the concentration rose sharply during the wet season (mean 7. total phosphates (0. the null hypotheses was rejected at significant levels tested (P ≤ 0.482 mg/L wet season canals water (Table 4. Fe: -0. This phenomenon is seen from the negative linear correlations of dissolved oxygen with heavy metals in Table 4.4.05) (Table 4.537.602.861) and NO3-N (0.1 and 4.5). 1979) hence making the water not suitable for domestic use or unsuitable for aquatic plants and animals. The dissolved oxygen in canals water wet season (3.4. Zn: -0. it is assumed that they were the major source of the phosphates. There was an indication of these contaminants being products of intensive farming in the farm where runoff water carry them to the canals that finally deposit them into River Kuywa during the wet season. These chemical activities can easily be seen from the positive linear correlations between COD and conductivity (0.778 ± 46.978).711.1 and 4. Clearly there was increase in chemical parameters in the water in the wet season leading to high oxygen demand.4.356.of heavy metals reduces oxygen concentrations in the water.975 mg/L) was well below the international standard mark of 4 – 5 mg/L (USEPA. Cu: -0.The distribution was skewed to the right (wet season).521 ± 75.743 mg/L wet season.4.556 ± 354. 4.1.4. The null hypothesis was rejected at testing level (P ≤ 0.861).885). From this observations.5).05) (Tables 4.4.4.
Nzoia.4.903) canals water showing their interrelationships.00 mg/L (EMCA.3).978 mg/L dry and 44. The variations per site and between seasons were significant at all the tested levels (Table 4. .957 ± 1.4.356 mg/L wet seasons canals water and for river water it was 2.phosphates in the canals water is beyond international standards of 2. 1979) was way far below the seasonal means.4.3 and 4. a clear indication that they came from similar origin. The canals water was extremely polluted with NO3-N at all times since the permissible limit of 10.00 mg/L (WHO. turbidity (0.1 and 4.1 and 4.326 ± 0.202 ± 22.214.171.124. 2006) and 0. 5). The concentration of NO3-N varied in a similar manner as that of total phosphates (Figure 4. It correlated strongly with conductivity (0. All the null hypotheses were rejected at all significant levels (Table 4.952 mg/L wet seasons (Table 4. COD (0.4.817). 4. This was an indication that they all came from similar origin. The data obtained show that the nucleus estate farms of Nzoia are a point source of nutrients into River Kuywa which finally will find its way into Lake Victoria through R. 1993 and USEPA. 4.906). 65 .4.929).517 mg/L dry and 25.4.3).3). Its mean concentration was 3. and total phosphates (0.4.152 ± 2.100 mg/L (USEPA. 1979).1.
Conclusions The use of nitrogenous fertilizers in sugarcane farming in Nzoia nucleus estate farms reduced soil pH that created acidic environment promoting heavy metal mobility. Once in the aquatic systems the heavy metals contributed to increased electrical conductivity. These findings were supported with the use of a control farm (a football pitch) within the same geographical region that did not practice sugarcane farming.Chapter 5 5. chemical oxygen demand and reduced dissolved oxygen of the water systems beyond allowable limits in some areas. The heavy metal burden in the aquatic environment within Nzoia Nucleus estate farms were within allowable limits as shown by levels in water and surface sediments in canals and River Kuywa. This acidic environment accelerated heavy metal solubility. the nitrogenous fertilizers themselves also found their way into the aquatic environment as was evident from high quantities of nitrate-nitrogen and total phosphates during the wet season. These quantities were above allowable limits hence posing a great threat to the environment as water systems may become eutrophic leading to serious problems like algal blooms and hyacinth growth.1. electrical conductivity and reduced the dissolved oxygen level during the wet season. bioavailability and mobility from one point to another. The heavy metals themselves are naturally occurring in Nzoia sugar belt as shown in the control site though the fertilizers used also contain contaminants of these heavy metals. leaching and erosion within the sugar plantations during the wet season acted as a transport media of the available heavy metals to the aquatic systems. 66 . Finally. 5.2. Reduction in soil pH within sugarcane plantations created an acidic environment that was evident in the aquatic systems and the analyzed soils within the nucleus resulting in high concentrations of heavy metals in wet season. Surface runoffs. The presence of heavy metals in the aquatic environment increased the chemical oxygen demand. solubility and bioavaillability in the aquatic environment. Summary Use of nitrogenous fertilizers in sugarcane farming reduces the soil pH in the farms.
Recommendations for future research There is need to screen sugarcane plants.3. total phosphates and turbidity. Other toxic heavy metals especially cadmium which is common in fertilizers to be studied so as to have a clear heavy metal burden of the River.Surface runoffs and erosion in the sugarcane farms is responsible for transportation of heavy metals and nutrients from the farms into the aquatic systems making the system polluted with total phosphates and nitrate nitrogen 5. 5. During the wet season. residents downstream River Kuywa are advised to avoid using the river water directly for domestic use for it is contaminated with physicochemical parameters including nitrate nitrogen. finished products from the factory. Recommendations The agricultural activities of sugarcane farming in Nzoia nucleus farms should go on but measures to be put in place to control acidification of the soil for this is affecting heavy metal burdens in the surrounding aquatic environments especially water quality in River Kuywa which is a source of domestic water. Heavy metals in the aquatic environment within the nucleus estate farms did not go beyond international standards. 67 . aquatic plants and animals from the farms in order to ascertain their heavy metal burden and potential effects so as to avoid intoxication in higher animals of the respective food webs.4.
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