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Department of Thematic Studies Campus Norrköping Bachelor of Science Thesis, Environmental Science Programme, 2017 Frida Enander Elemental distribution in the catchment around Lake Victoria in Kenya Linköpings universitet, Campus Norrköping, SE-601 74 Norrköping, Sweden

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Page 1: Elemental distribution in the catchment around Lake ...liu.diva-portal.org/smash/get/diva2:1112768/FULLTEXT01.pdf · ecosystem consisting of forests, fisheries, wildlife habitats

Department of Thematic Studies

Campus Norrköping

Bachelor of Science Thesis, Environmental Science Programme, 2017

Frida Enander

Elemental distribution in the catchment around Lake Victoria in

Kenya

Linköpings universitet, Campus Norrköping, SE-601 74 Norrköping, Sweden

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Titel Title: Elemental distribution in the catchment around Lake Victoria in Kenya Författare Author: Frida Enander

Rapporttyp Report category Licentiatavhandling Examensarbete AB-uppsats C-uppsats D-uppsats Övrig rapport ________________

Språk Language Svenska/Swedish X Engelska/English ________________

Sammanfattning Victoriasjön som är världens näst största sötvattensjö är drabbad av en ökande övergödning, främst beroende på mänskliga aktiviteter. I

denna studie har spridningen av sex grundämnen (Cu, Zn, N, C, P och Si) studerats i sediment från fem olika platser i Kenya; Busia,

Kapsabet, Siaya och från två platser i Kisumu. Förändringar i spridningen av de olika ämnena sattes i relation till historiska händelser i

upptagningsområdena för att undersöka om dessa hade en påverkan på övergödningen i sjön. Beräkningarna visade på starka samband

med mänskliga aktiviteter och markanvändningen med utbyggnad av järnvägen, ändrade jordbruksmetoder och tillväxt av tätorter.

Dessa förändringar har satt tydliga avtryck i spridningen över tid av de grundämnena som mätts. Spridningen är korrelerad med

förändringar i sjöns trofiska tillstånd. Det är också en tydlig skillnad i spridningen av de studerade ämnena från urban miljö respektive

landsbygd.

Abstract Lake Victoria, the second largest freshwater body in the world is affected by rise in eutrophication. This is mainly due to anthropogenic activities

happening in the catchment. In this study, distribution of six elements (Cu, Zn, N, C, P, and Si) in sediments were studied from the five sites in

Kenya namely Kisumu (DK2, OK2), Busia (KK2), Siaya (SPK2 and Kapsabet (KP1A). The elemental flux values were correlated with historical

changes in the catchment to see if it can influence the eutrophication in Lake Victoria. Flux calculated for these elements show a strong correlation

with anthropogenic activities associated with land-use changes ushered after building of the railroads, agricultural practices and urban development

in the catchment. The spatial and temporal changes in distribution of these elements have a distinct signature on the metal flux. The metal flux are

correlated with change in trophic conditions in the lake. There is also a distinct difference in metal flux into the lake derived from urban versus

rural areas.

ISBN _____________________________________________________ ISRN LIU-TEMA/MV-C—17/20--SE _________________________________________________________________ ISSN _________________________________________________________________ Serietitel och serienummer Title of series, numbering Handledare Tutor: Joyanto Routh

Nyckelord Keywords: Lake Victoria, Eutrophication, Sediment, Elemental flux.

Datum Date: 2017-06-16

URL för elektronisk version http://www.ep.liu.se/index.sv.html

Institution, Avdelning Department, Division Tema Miljöförändring, Miljövetarprogrammet Department of Thematic Studies – Environmental change Environmental Science Programme

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Table of Contents Acknowledgement.............................................................................................................1

Sammanfattning.................................................................................................................1

Abstract.................................................................................................................................2Introduction........................................................................................................................3Aimsandobjectives.....................................................................................................................4Studyquestion...............................................................................................................................5

Background.........................................................................................................................5SedimentandenvironmentalcharacteristicsinLakeVictoria...........................................7Previousstudies.......................................................................................................................................8

Signsofeutrophication..............................................................................................................10Geochemistryofelements(Cu,Zn,N,C,PandSi)................................................11CuandZn......................................................................................................................................11N.....................................................................................................................................................12C......................................................................................................................................................13P......................................................................................................................................................14Si.....................................................................................................................................................15

Materialsandmethods.................................................................................................16Samplinglocationsanddescription..............................................................................................16

Limitations........................................................................................................................19Results................................................................................................................................20DK2:urbanarea..........................................................................................................................20OK2:urbanarea..........................................................................................................................21KK2:agriculturearea.................................................................................................................23SPK2:agriculturearea...............................................................................................................24KP1A:agriculturearea..............................................................................................................26

Discussion.........................................................................................................................26Zn...................................................................................................................................................27Cu...................................................................................................................................................28N.....................................................................................................................................................30C......................................................................................................................................................32P......................................................................................................................................................35Si.....................................................................................................................................................36

Dometalfluxesinfluenceeutrophication?............................................................38Conclusions.......................................................................................................................40

Validationandreliability.............................................................................................41

Furtherstudy...................................................................................................................41References........................................................................................................................42

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Acknowledgement First of all, I want to thank my supervisor Joyanto Routh for supporting and advising

me in my study. I am also very grateful to Mårten Dario for his help in the lab and to

Per Sandén who helped me with Excel and to get a better understanding of the data. I

also want to thank Moses Odhiambo who helped me with information about the study

sites and other details. And finally I want to thank Åsa Danielsson who guided me

with the statistical analyses.

Sammanfattning Victoriasjön som är världens näst största sötvattensjö är drabbad av en ökande

övergödning, främst beroende på mänskliga aktiviteter. I denna studie har spridningen

av sex grundämnen (Cu, Zn, N, C, P och Si) studerats i sediment från fem olika

platser i Kenya; Busia, Kapsabet, Siaya och från två platser i Kisumu. Förändringar i

spridningen av de olika ämnena sattes i relation till historiska händelser i

upptagningsområdena för att undersöka om dessa hade en påverkan på övergödningen

i sjön. Beräkningarna visade på starka samband med mänskliga aktiviteter och

markanvändningen med utbyggnad av järnvägen, ändrade jordbruksmetoder och

tillväxt av tätorter. Dessa förändringar har satt tydliga avtryck i spridningen över tid

av de grundämnena som mätts. Spridningen är korrelerad med förändringar i sjöns

trofiska tillstånd. Det är också en tydlig skillnad i spridningen av de studerade

ämnena från urban miljö respektive landsbygd.

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Abstract Lake Victoria, the second largest freshwater body in the world is affected by rise in

eutrophication. This is mainly due to anthropogenic activities happening in the

catchment. In this study, distribution of six elements (Cu, Zn, N, C, P, and Si) in

sediments were studied from the five sites in Kenya namely Kisumu (DK2, OK2),

Busia (KK2), Siaya (SPK2 and Kapsabet (KP1A). The elemental flux values were

correlated with historical changes in the catchment to see if it can influence the

eutrophication in Lake Victoria. Flux calculated for these elements show a strong

correlation with anthropogenic activities associated with land-use changes ushered

after building of the railroads, agricultural practices and urban development in the

catchment. The spatial and temporal changes in distribution of these elements have a

distinct signature on the metal flux. The metal flux are correlated with change in

trophic conditions in the lake. There is also a distinct difference in metal flux into the

lake derived from urban versus rural areas.

Keywords: Lake Victoria, Eutrophication, Sediment, Element flux.

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Introduction Lake Victoria is the second largest freshwater body in the world and it is shared by

five countries Uganda, Kenya and Tanzania, Rwanda and Burundi. The lake plays an

important role since it directly supports around 30 million people in East Africa

(Martins 2015; Corsi et al. 2006; Awange and Obera, 2007; Encyclopædia Britannica,

2014). Fisheries and power generation in the Lake Victoria region are the main

drivers of the local economy. Likewise, the industries are also expanding rapidly in

the region (Martins, 2015).

The Lake Victoria basin has the richness of a unique terrestrial and biodiversity

ecosystem consisting of forests, fisheries, wildlife habitats and wetlands. People

living around the lake make their living mainly from the fishing and its production is

estimated at 400 million USD annually (Corsi et al. 2006). There are more than 200

fish species in Lake Victoria. However, Tilapia and Nile perch are the most common

variety that are widely exported as part of the commercial catch and export

(Bergwerff, Seinen & Werimo 2009).

Water from Lake Victoria is used for agriculture, as well as for domestic and

industrial purposes and recreation activities (Bergwerff et al., 2009). The increase in

the population in the catchment has led to an increase of various activities and

associated pollution. This has caused serious environmental problems in Lake

Victoria such as loss of biodiversity, exploitation of resources and deterioration of

water quality (Corsi et al. 2006). During the last few decades, Lake Victoria has

undergone profound ecological changes (Brown et al. 2002) and it suffers from

problems such as high pollution and overfishing (Martins 2015). This has increased

the tropic status and various parts of the lake are already eutrophic (LVEMP, 2012;

Bergwerff, Seinen & Werimo, 2009).

Different types of elements associated with eutrophication are derived from

anthropogenic activities, and they accumulate in sediments. An evidence for this, are

trace metals in sediment derived from industries and other agricultural activities in the

lake´s catchment (Cui et al. 2014).

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Furthermore, the polluted water from the catchment and rivers that drain in to the lake

caused increased input of nutrients and sediments (Bootsma, Hecky & Odada, 2006).

Das, Supriyo Kumar et al. (2008) said that urban lakes are more vulnerable to trace

element pollution and it is because of widespread cultural activities that are in the

catchment. Metals that have been taken up and deposited can be remobilized and

redistributed into the water column and sediments (Mwamburi, 2013). The mobility

and toxicity of metals is species-dependent and how much elements are biologically

available depend on concentrations of the chemical species in the water column and

sediments. The biological availability is also influenced by the physical and chemical

conditions (Mwamburi, 2013). However, in natural ecosystems sediments play an

important role because it buffers the high metal concentration in water by absorption

(Khairy et al.2014). Moreover, Cazier et al. (2015) said that elevated concentrations

of trace metals in sediments are a sign of anthropogenic pollution rather than natural

enrichment due to geological weathering or high background concentrations that are

more restricted in distribution.

Aims and objectives There have been significant changes in landscape and anthropogenic activities that

have historically increased in the catchment of Lake Victoria. It is known that Lake

Victoria is slowly becoming more eutrophic and many studies that have been done in

this water body have firmly established the change in its trophic status (Corsi et al.

2006; Bergwerff, Seinen & Werimo, 2009). These studies focused on water quality,

fishes, macrophytes, changes in chemical and physical environment within the lake

(Mwashote & Shimbira, 1994; Ayia et al., 2012).

Few studies exist on elemental distributions in the lake sediments and its catchment.

Therefore, we will investigate the factors that drive the eutrophication in Lake and

what is happening in the catchment that influence eutrophication in the lake. This will

be done by studying the elemental distribution in the sediment samples. The elemental

trends in sediments will be used to monitor if there is an impact of anthropogenic

pollution in the lake.

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We will investigate the elemental flux for copper (Cu), zinc (Zn), nitrogen (N),

carbon (C), phosphorus (P), and silica (S) that can be related to historical changes in

the catchment and eutrophication in Lake Victoria. These elements were chosen

because they are essential for living organisms and plants, and their metabolic

processes (Wetzel, 2001; Yang et al. 2015). Some of these elements are derived from

anthropogenic sources (Das, Supriyo Kumar et al., 2008), and their distribution

pattern can provide information about land use changes in the catchment. In order to

investigate what is the net flux of these metals and other nutrients derived from the

catchment that make its way into the lake, and drive eutrophication, sediment cores

were retrieved from several relevant locations from the Kenyan side of the lake (Fig.

2). The elemental flux (g/cm2/year) will provide information about the input rate, fate,

and changes in its deposition pattern, and supposedly indicate what is happening in

the catchment from a historical perspective (Kang, R., Zhang, X., Wang, J & Wang,

Z., 2017).

Study question

Can elemental fluxes (Cu, Zn, N, C, P, Si) be related to historical changes in the

catchment that influence eutrophication in Lake Victoria?

Background This study is a part of an ongoing project on paleo-climate reconstruction in Lake

Victoria basin. Several sediment cores were retrieved from key locations around the

lake (upland to lowland levels) which are being investigated for various physical and

geochemical proxies to establish the ongoing climatic changes, land-use changes,

anthropogenic activities and other historical changes that are preserved in the

sediment record.

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Lake Victoria Lake Victoria, during the last few decades, has been undergoing large ecological

changes (Brown et al. 2002) due to various anthropogenic activities (Corsi et al. 2006)

in the catchment, e.g. motor vehicles, industries, agriculture and agrochemical

factories (Awange and Obera, 2007). Furthermore, the authors stated that apart from

these factors, atmospheric depositions, mainly from biomass burning, is also

suggested to be a major pathway driving eutrophication in Lake Victoria (Odihambo

and Routh 2016). Atmospheric pollution contributes more than 30% of nutrients into

the lake (Awange and Obera, 2007).

Because of precipitation and direct atmospheric input, the nutrient budget in the lake

has varied. For example, the atmospheric input contributes about 55% of total

phosphorus loading and 65% of total nitrogen in Nyanza Bay (Gikuma-Njuru et al.

2013).

The population of Lake Victoria basin (LVB) has grown in 1932 from 4.6 million to

27.7 million in 1995, and later to 30 million people, which can be explained by the

introduction of railroads in east Africa that opened the Lake Victoria region to

largescale resettlement (Brown et al. 2002). The settlements led to plantations and

increased agriculture for export of commercial crops.

The population grew caused by immigration and improved healthcare facilities that

raised life expectancy putting further stresses on the resources. This led to further

expansion of agricultural activities and large-scale deforestation that are still ongoing

(Brown et al. 2002). In addition, the introduction of Nile perch (Brown et al. 2002;

Hecky, 2010) and its rapid increase in population from 1970 to early 1980s led to the

rise of an export based fishing industry (Hecky, 2010). This contributed positively

towards the growing economy around the lake and further population rise. See Fig.1

(Brown et al. 2002).

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These historical changes in the catchment caused an appreciable rise in chemical flux

from land-use changes and energy consumption. Human activities such as household

and industrial activities that increase pollution, problems with medical waste disposal

and recreation have an impact on water bodies (Frumin & Gildeeva, 2014).

Consequently, water bodies can become eutrophic over the years, and this leads to

various environmental challenges for management and sustainability issues (Shan &

Zhang, 2008). Brown et al. (2002) indicated that changes in phytoplankton

community seem to be a logical consequence of excess nutrient loading from

deforestation and intensive agriculture.

Figure 1.“Principal events in the recent environmental history of Lake Victoria, in relation to human-population growth and agricultural production in its drainage basin” (Brown et al, 2002). The population of Lake Victoria started to grow 1932 when the railroad arrived in Kampala, Uganda. The figure shows the introduction of Nile perch 1954 (Brown et al. 2002).

Sediment and environmental characteristics in Lake Victoria Lake sediments consist of organic matter in different stages of decomposition,

particulate mineral matter and clays, carbonates and silicates (Wetzel, 2001).

The regional geology surrounding Lake Victoria consists of rocks of the Nyanza

system, sediments, lavas and volcanic rocks.

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The southern and northern catchment with a total area of 47 164 km2 are drained by

small and large rivers, and they are important transport channels for terrestrial inputs

draining into the lake.

Increasing silt in Lake Victoria are coming from expanding agricultural activities and

unsuitable land management methods. Moreover, external and internal activities

represent the major influencing factors, which reflect the water quality of the lake and

have also been linked to eutrophication (Mwamburi, 2013). Main industries are coffee,

sugar and tea in the highland and lakefront areas.

Previous studies Previous studies in Lake Victoria have focused on fishes and water quality issues

(Ayia et al, 2012). One of these studies, focused on monitoring environmental

pollution on fishing that was conducted by the Lake Victoria Environmental

Management Project (LVEMP),inWinamGulfandtheoffshorereachesofLake

VictoriaintheKenyanwaters(LVEMP, 2012a).Theaimofthemonitoringexercise

wastogetabetterunderstandingofthevariabilityinnutrientlevels.Itwasthought

thatthiswouldguidethemanagementactioninLakeVictoria(LVEMP, 2012a). The

main emphasis in this study was to reduce the environmental stress in Lake Victoria

Basin, from catchment derived pollution and eutrophication problem.

The conclusions of the LVEMP study are summarized below:

• Lake Victoria became polluted and has undergone eutrophication due to

anthropogenic activities around the lake margins and rivers draining into the

lake.

• The water had high nutrients levels, especially phosphorus. In addition, the

surface sediments contain a significant amount of metals e.g. Cu, Zn, Pb and

Ni. Waters within the gulf have a poor quality compared to the open water.

The railroad in 1900s that was built extending it from Kisumu, Kenya (Hecky, 2010)

to Kampala, Uganda 1932 (Brown et al. 2002) increased the pressure in the lake.

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The railroad from Mombasa to Kampala through Kisumu opened the Lake Victoria

basin to traffic and movement that was restricted earlier. This caused various

environmental and human pressures (Brown et al. 2002). Furthermore, the rail linked

to Nairobi and the coast made it possible ferrying the fresh caught fish to large

commercial centres for local consumption and export. This also led to overfishing in

the lake and a gradual change in its tropic state (Hecky, 2010).

Agriculture and extensive forest clearance before 1950 for conversion to farmland to

valued crops increased pressures on land and the waterbody. In 1962-64, there was a

three years period of heavy rainfall (Bootsma, Hecky & Odada, 2006; Hecky, 2010),

this resulted in coastal flooding, but had little impact on lake sediments. During 1970s,

inshore primary productivity increased, resulting in high C flux in the water column,

that was further amplified by the increasing internal P-loading from the hypolimnetic

anoxia (Hecky, 2010).

Another stress on the water body was from the motor vehicular traffic. The motor

vehicle pollutants entered the lake waters directly or from surface runoffs (Awange

and Obera, 2007). Pollutions from runoffs is from litter generated from bus terminals

and open car repair garages, exhaust, oil spills on roads and oil from petrol stations

which finds its way into the lake. There are urban centres and two cities that

contribute to increasing vehicular contamination. Kisumu and Homa Bay in Kenya

along with Kampala in Uganda and Mwanza in Tanzania have been blamed for high

pollutant input from settlements and industries along the lake margin (Awange and

Obera, 2007).

Most of the household and small industrial wastes end up in drains and during

rainstorms, they are swept into the lake. Particularly, detergents used for washing

vehicles, runoff from garages and paints contain high phosphorus levels that

end up in Lake Victoria (Awange and Obera, 2007). The poor infrastructure of

drainage network further contributes to the problem.

Consistent with this, increase in P-load, primary production, changing diatom

community and declining hypolimnetic oxygen concentration was recorded in lake

sediments from 1960s to the 1980s (Hecky, 2010).

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Besides human impact, climate change is also recognised to affect the rift valley lake

systems. Poor ventilation and mixing in the deep water in Lake Victoria suggest to

greater increase in oxygen depletion in the 1980s compared to 1960s (Hecky, 2010).

Africa is judged to have the highest rate of biomass burning in the world, resulting

from expansion in agriculture and crops land, and household use of biomass for

cooking and heating. Biomass burning results in atmospheric deposition of nutrients

(mainly as precipitation) into the lake that increases eutrophication.

Thus, external P-loading from rainfall is one of the dominant external input of P and

N sources into Lake Victoria. Furthermore, since N, P and Si, are retained in the lake

(Bootsma, Hecky & Odada, 2006) it results in seasonal diatom blooms. Some of these

early blooms coincide with increase in Si concentration from 1930 to the middle of

1980s and diatom production (Brown et al. 2002).

Signs of eutrophication Availability of limited historical data on water and sediment quality during this

critical period makes the documentation of trophic shifts unevenly distributed around

the lake. Moreover, different trophic indicators have been used to evaluate

eutrophication, which led to the uncertainty in assessment of these changes in the lake

(Cumming et al. 2009).

Literature review indicates that during 1904-1905 and 1927-1928, cyanobacterial

blooms were first reported in Lake Victoria. During these period, the lake was

classified as eutrophic by Worthington (1930). Furthermore, anoxic bottom sediments

were also present both inshore and offshore. Lake Victoria was reported to have

anoxic waters as noted during investigations during 1960-70 (Verschuren et al. 2002;

Brown et al. 2002). Further, Cumming et al (2009) indicated that cyanobacteria had

taken over the diatom communities since 1960, while Brown et al (2002) indicated

the dominance of cyanobacterial occurred since the late 1980s.

Gikuma–Njuru (2013) indicated that it is common in the main lake that the

dominance between diatoms and cyanobacteria vary seasonally.

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By the 1960s, phosphorus concentration and primary production increased in the lake

(Cumming et al.2009).

A palaeolimnological study by from Brown et al (2002) indicated that increase in

phytoplankton production developed in the 1930s in Lake Victoria, and at the same

time human population and agriculture activities also increased in the Lake Victoria

basin (Brown et al 2002). However, Cumming et al. (2009) indicated that Si

concentrations in Lake Victoria declined by 80% during the late 20th century and this

could be linked to rise in diatom population and human activities in the catchment.

Geochemistry of elements (Cu, Zn, N, C, P and Si)

Cu and Zn Minor amounts of Cu and Zn are required for nutrition of plants and animals (Wetzel,

2001), and hence they are classified as essential elements for all living organisms

(Gachanja et al. 2014). Cu and Zn for example, are mostly derived from

anthropogenic sources such as fertilizers, agricultural waste, runoff, industries and

from sewage input (Das, Supriyo Kumar et al., 2008). Cu is used as an aquatic

herbicide to reduce algal growth. It is also applied in antifouling paints which is used

on boat hulls (Gachanja et al. 2014). These metals can also enter lakes through

leaching of effluents and dry deposition (Mwamburi & Nathan Oloo, 1996).

Bacteria, plants, algae, planktonic and benthic organisms take up dissolved metals,

such as Cu and Zn, directly. Cu is more toxic to lower aquatic organisms and

phytoplankton (Gachanja et al. 2014). Zn mostly occurs in its ionic form or as weak

complexes and can be tolerated more by living organisms (Wetzel, 2001). Notably,

organic ligands together with Cu and Zn form strong complexes and many of these

compounds are produced by algae (Gachanja et al. 2014) These metals can also

adsorb to particulate matter in the water column and then, enter aquatic organisms.

They become bioavailable to organisms e.g. after deposition and translocation from

different point source (Mwamburi & Nathan Oloo, 1996).

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N N is an abundant nutrient and the fourth most abundant element in cellular biomass

(Wetzel, 2001). N is also the major element in the atmosphere (Klotz & Stain, 2016).

However, availability of N is limiting for living organisms, and < 2% N is often

limiting to plant growth (Wetzel, 1983). N is bonded to C, O and H in compounds like

NOx NHx and in form organic N. The latter are created, largely, by biological nitrogen

fixation of unreactive N which is (triple-bonded N2). N in fresh waters occurs in

different forms: N2, organic compound from amino acids, recalcitrant humic

compounds, ammonia (NH4+), nitrate (NO3) and nitrite (NO2

-). Other sources of N

are: N fixation in water and sediments, atmospheric precipitation of N, and N inputs

from surface and groundwater drainage (Wetzel, 2001). The increasing N-input from

atmospheric sources is significant for productivity, and the N-cycle (Wetzel, 2001). In

areas that are not polluted, the common form N in the atmosphere is NH4, and it is

mostly derived from decomposition of terrestrial organic matter. However, N

deposition from atmospheric sources, in generally, has been considered to be minor

compared to direct terrestrial runoff. N loss occurs by reduction of NO3 to N2 caused

by bacterial denitrification which later returns N2 to the atmosphere (Wetzel,2001).

When significant amount of sedimenting organic matter reaches hypolimnion in a

stratified lake, NH4 –N can accumulate; this fraction will continue to accelerate while

the hypolimnion becomes anoxic. Moreover, a large amount of NH4 is adsorbed to

sediment particles. During sedimentation, denitrification can result in major losses of

N. In particular, when sufficient amount of light reach the sub-surface sediment, it is

enough to support benthic algal and cyanobacterial life to assimilate NH4 –N from

interstitial water. This prevents the flux of NH4 –N from the sediments into the water

column (Wetzel, 2001). However, approximately, half of the water-soluble organic N

compounds are derived from urea. In lakes in hypolimnion, under anaerobic

condition, NO2-N concentration will increase under reducing condition (Wetzel,

2001).

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C Carbon is essential for all living organisms and is needed for metabolism (Wetzel,

2001; Yang et al. 2015). Carbon dioxide (CO2) is a primary source of C during

photosynthesis and results in generation of organic substances. Respiration on the

other hand produces influx of CO2 and HCO3 by most organisms (Wetzel, 2001).

Organic carbon-based compounds provide important substrates and energy during

metabolism. Carbon is divided into organic and inorganic carbon compounds.

Inorganic carbon is largely referred to as dissolved carbon dioxide and bicarbonate

(HCO3), while organic carbon is derived from organic matter existing in soil and

water and derives from plants, microorganisms and animal products that are in

different stages of decomposition. The majority of organic carbon that is coming from

natural water consists of dissolved organic carbon (DOC) and dead particulate organic

carbon, POC (Wetzel, 2001).

Organic matter consists of C bonded to other elements such as hydrogen (H), N,

oxygen (O), P and sulphur. Sources for OC emitted to the atmosphere are; 1)

Biogenic i.e. emissions from natural systems such as organic compounds, airborne

particles, emissions/gas from water or volcanos. 2) Anthropogenic i.e. emissions

from human activity such as fossil combustion for energy, use of solvents and

pesticides. Emission from burning biomass can come from both natural processes as

well as from human activity. (Boyer, De Waller and Lavorivska, 2016). Biomass

burning leads to input of organic and inorganic forms of C into the atmosphere and

aquatic bodies, and they have similar physiochemical properties. 60 % of the global

OC flux is in form of wet deposition and 40% in dry form. Most, 90%, of the wet

atmospheric deposition flux is dissolved organic carbon, DOC. 90% of the OC comes

from terrestrial ecosystems and 30-50% of the OC is deposited into the oceans. Wet

deposition function as a sink for emissions from incomplete combustion of fossil fuels.

This is a human disturbance in the C-cycle. (Boyer, DeWaller and Lavorivska, 2016).

Both lake sediments and soils are known for storage of OC. The sedimentation of OC

that reach the sediment surface can originate from internal primary production or

derived from the catchment that has contrasting properties.

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Temperature plays a role in controlling sediment OC mineralization and also other

factors as pH, humidity, nutrients and oxygen in complex systems (Gudasz et al.

2015).

P P is included in organism’s DNA and RNA, adenosine 5-triple phosphate (ATP),

mineral phases of rock and soil and phosphoproteins. P is also adsorbed onto dead

particulate organic matter. It is essential for living organisms because compounds that

containing P influence, almost all types of metabolism. In particular, it is very

essential during photosynthesis when energy transformation of phosphorylation

reactions happen. P is the least abundant element required for algal growth of fresh

water (Wetzel, 2001; Ni & Wang, 2015). However, P is like a cornerstone for algal

metabolism and growth (SMHI, 2014; Wetzel, 2001).

The importance of P as a nutrient that accelerates productivity in fresh waters has

been paid more attention compared to the P pool in sediments. In this context, it is

important to point out that lacustrine sediments contain much higher P concentration

than water and P exchanges between sediments and overlaying water are included in

the major P cycle in natural waters and there is also an apparent net movement of P

into the sediments in main lakes. P-levels in fresh water increase in lowland waters,

and is derived from sedimentary rock deposits. Most of the total phosphorus (TP) is in

the organic phase and at least 70% of total organic P is within the particulate organic

material (Wetzel, 2001). How rapidly the different processes regenerate P back to the

water depend upon several factors. The factors are e.g. biological, physical and

chemical factors (Wetzel, 2001).

P is the least abundant element in fresh water because, after plants decomposition, P

will be taken up rapidly by other plants in the aquatic ecosystem (Wetzel, 2001), and

it can also be explained by the high reactivity with organic and inorganic compounds

which results in low content of P in sediments (Gikuma-Njuru, Guildford & Hecky,

2009). Large quantities of nutrient losses in lakes are stored in parts of the ecosystem,

which are not easily available to aquatic producers.

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15

One of these factors is sedimentation of P minerals that are imported from drainage

basin. The majority of these minerals settle rapidly and deposit in nearshore areas

(Wetzel, 2001). During cell breakdown and decomposition, most of P in algae are

released during bacterial degradation (Wetzel, 2001).

P in atmospheric precipitation and particulate material come from fine particles of soil

and rocks that are derived from living and dead organisms. This P is primary in the

form of volatile compounds caused from natural fires, burning of fossil fuels and

release from plants. However, the amount of P in precipitation is generally less than N

precipitation and the major sources of P, from inland regions in precipitation, is from

dust that generated from land caused by soil erosion, industrial and urban

contamination of the atmosphere. Furthermore, soil surface contains quite a lot of

organic P from degradation of plant matter in various stages (Wetzel, 2001).

Si Silica is essential for diatoms, alga and some higher aquatic plants. Si is a major

source of influence in algae production in lakes and diatoms utilize Si to control flux

rates in streams and lakes. Availability of Si can have a strong influence on

productivity in lakes. However, Si is a natural element derived from degradation of

aluminosilicate minerals and rocks. Si-loadings in lakes are usually from influent

surface waters that are derived from rivers (Wetzel, 2001).Si plays an essential role in

the aquatic bodies because diatoms require this element for its growth, and diatoms

form a major portion of planktonic primary producers.

Diatoms are the largest producer of biogenic silica (BSi) in surface waters. They also

function as a transporter for carbon (Cotten et al, 2006). BSi is derived from higher

plants and they are siliceous, which in turn, make the soil contain BSi which if

mobilized can influence productivity in the water column. When the plants’ roots take

up the dissolved silicate, then they deposit it further to produce phytoliths and

phytoliths are silicified structures. After plants break down the phytoliths, it will

release Si into the soil and accumulate in the upper soil layers (Conley et al, 2005).

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Si in diatoms usually settle into sediments and this biochemical condensation of

dissolved Si together with sedimentation exceeds inputs to the sediments from living

organisms. Furthermore, these inputs reaching the sediments vary periodically. The

rate of Si release, coming from sediments, depends on the temperature in water and

differences in silica concentration in sediments and the overlying water (Wetzel,

2001). Si concentration in water increases when the pH declines below 7 and is above

9; Si concentration decreases between pH 7 to 9. In fresh water, Si concentration

increases at higher temperatures (Wetzel, 2001).

Materials and methods

Sampling locations and description We have analysed selected elements in sediment cores retrieved from the catchment.

The sediment cores were retrieved from five locations around Lake Victoria: two

cores from Kisumu, the third largest city, one each from Siaya and Busia in the Nandy

highland region that is mostly rural and finally from Kapsabet, an agricultural area in

the Riff Valley.

The locations, codes and length of cores:

The locations of the sample sites are;

• Kisumu1, urban area (DK2; 56 cm), 0° 7'59.94"S 34°44'57.24"E, Kenya

• Kisumu2, urban area (OK2; 92 cm), 0° 8'29.04"S 34°36'9.30"E, Kenya

• Siaya, agriculture area (KK2; 32 cm), 0° 4'7.50"N 34° 7'43.98"E, Kenya

• Busia, agriculture area (SPK2; 92 cm), 0°10'32.74"N 34° 0'23.80"E, Kenya

• Kapsabet, agriculture area (KP1A; 88-96 cm), 0° 2'34.85"N 35° 4'50.42"E,

Kenya

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17

Figure 2. Lake Victoria regions with the five samplings locations.

The sediment cores were retrieved, taken and handled by VR-SRL project team and

the laborating and analyzing was done at Linköpings university.

All the sediment cores from the sites (Kapbsabet) were taken with a motorized Vibra

corer. However, KP1A was retrieved with a hand held Russian (peat) corer. The cores

were stored in a freezer at -200 C after they had been sliced at 1cm interval. The

samples from each site; DK2 (Kisumu highland), KP1A (Kapbsabet), SPK2 (Busia),

KK2 (Siaya), OK2 (Kisumu) were freeze-dried in plastic bags at -55 0C for 48 hours.

In order to assess the chronology, the sediments were dated using the 210Pb

methodology at the Great Lakes Institute, University of Milwaukee (USA). Details of

this is beyond the scope of the present work and have been discussed elsewhere

(Odhihambo & Routh, 2016). Age and sedimentation rates proposed for each

sediment core in the previous study (Odhihambo, 2016) are reported herein to

evaluate the metal flux.

Busia

Siaya Kisumu

Homa Bay

Kapsabet

Gulf Nyanza

A. Kenya

Lake Victoria

Figure 2. Sampling locations in the Kenyan (A •) waters as included in this study from Lake Victoria

and its catchment. The five sampling sites were the sediment cores were retrieved DK2, OK2, KK2

and SPK2 at lower elevation and KP1A at higher elevation. Homa Bay was excluded from the study.

were the sediment cores were retrieved.

B A

Tanzania

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18

The elements in the sediment cores were analyzed by using X-ray fluorescence (XRF).

This is a core scanner which provides the elemental content in sediment samples.

The XRF

Photo: Frida Enander The sediment was poured out on a plastic bag and placed on the lead plate. The XRF

settings were set on Application GeoChem mode. When the analyses were done, the

XRF was held straight above the samples. The analyse time was 60 seconds at each

spot which was considered sufficient.

Calculation of metal flux The metal flux was calculated in the sediment cores based on the concentration of

specific metal (%) in the sediment layer at specified depth using the XRF, mass depth

(g/cm) and sedimentation rate (cm/year; Donato et al. (2016). An example how this

was calculated for Zn is provided below:

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19

Zn concentration (%) = 0.018

Mass depth = 0.75 g/cm

Sedimentation rate = 0.056 cm/year

The layer

1) (0.018 X 0.75) / 100 = 1,35 E-4

Aprox age

2) 0.75/ 0.056 = 13.39

Accumulation g/cm2/ Year

3) (1,35 E-4 x 1000) / 13.39 = 0.01.

The metal flux (Zn) = 0.01g/ cm2 / year

Limitations There were six sampling sites that were investigated for elemental accumulation, but

Odhiambo (2016) indicated that HK2 in Homabay did not have reliable sedimentation

rate and its dating was inconclusive due to natural mixing in the sediments. This is

due to its proximity to farmlands and the fact that soils had been tilled for farming.

Hence, HK2 was not measured. Flux for C and N for site KP1A will not be included

because of inconclusive sediment rate. All elements flux for each sites are not

included because of too few values.

Because of the difficulty to define the ages in sediment cores that contain lead 210Pb

going back to more than 150 years, the focus will be on the sediment history that goes

back as far as 1860, (which is more than three half lives of 210Pb). Because

extrapolation of 210Pb dates too far back in time (~120 yrs) is not supported, the

discussion in this study is restricted to events up to the 1800s.

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20

Changes in the lake before this period are not connected to human activities since

access within the lake’s catchment was restricted. These changes are therefore

assumed to be mostly from natural processes, erosion and weathering.

Results

The metal accumulation flux in sediments have large variations as indicted below.

DK2: urban area Figure.3. shows the elements Zn, N, C and Si at site DK2 which is 56 cm in depth.

The highest and the lowest flux for Zn are 0,01 g/cm2/year and 0,0005 g/cm2/year,

respectively. The graph for Zn shows three extreme values and they are 0,001

g/cm2/year, 0,009 g/cm2/year, 0,002 g/cm2/year. The highest and the lowest values for

N flux are 1,19 g/cm2/year and 0,06 g/cm2/year, respectively. There are two extreme

values, which show up in the core, 0.06 g/cm2/year and 1.19 g/cm2/year.

The highest and the lowest flux of C are 0,75 g/cm2/year and 3,40 g/cm2/year,

respectively. There are four extreme values, which occurs in the core that are 3,4

g/cm2/year, 0,75 g/ cm2/year, 1,36 g/ cm2/year, 2,38 g/ cm2/year. The highest flux of

Si is 13,9 g/cm2/year while the lowest value is 4,50 g/cm2/year.

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21

Figure 3. Zn, N, C and Si flux at site DK2.

OK2: urban area Figure 4 shows the distribution of elements, Cu, Zn, N, C, P and Si. Because the

elemental concentrations are high at 40 cm they are divided by 10 and 100

respectively to smoothen the graph.

The highest flux for Cu is 2,90 g/ cm2/year and lowest values 0,04 g/cm2/year. The

highest and the lowest flux for Zn are 0,52 g/cm2/year and 0,06 g/cm2/year,

respectively. The trend shows one extreme value at 5,16 g/cm2/year for Zn.

The flux for N values varies from 0,5 g/cm2/year to 1 g/cm2/year. The highest and the

lowest values are 3,54 g/cm2/year and 0,42 g/cm2/year, respectively. There are two

extreme values 35,5 g/cm2/year and 3,42 g/cm2/year, respectively.

1531

1631

1731

1831

1931

11

21

31

41

51

0,6 0,9 1,2 1,5 1,8 2,1 2,4 2,7 3 3,3 3,6

yea

rs

Dep

th,c

m D

K2

C. g/cm2/year

1531

1631

1731

1831

1931

11

21

31

41

51

0,005 0,205 0,405 0,605 0,805 1,005 1,205

yea

rs

Dep

th

,cm

DK

2

N. g/cm2/year

1500

1600

1700

1800

1900

200010

20

30

40

50

60

0,0003 0,0023 0,0043 0,0063 0,0083 0,0103

Years

Depth,cmDK2

Zn. g/cm2/year

1500

1550

1600

1650

1700

1750

1800

1850

1900

1950

20003 5 7 9 11 13 15

Years

Dep

th,

cm D

K2

Sio2. g/cm2/year

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22

The highest and the lowest flux for C are 56,1g/cm2/year and 6,34g/cm2/year,

respectively. The highest and the lowest values for P are 0,68 x100 g/cm2/year and

0,28 g/cm2/year, respectively. The three extreme values are 1,58 g/cm2/year, 0,28

g/cm2/year and 68,37 g/cm2/year, respectively. For Si the highest and lowest flux are

11978 g/cm2/year and 127 g/cm2/year, respectively.

Figure 4. Cu , Zn, N, C, P and Si flux at site OK2. Note that N is divided by 10 and for Cu, P and Si are divided by 100 to smoothen the graph.

18801895191019251940195519701985200020150,1

15,1

30,1

45,1

60,1

75,1

90,1

105,1

4 9 14 19 24 29 34 39 44 49 54 59

yea

rs

dep

th,c

m O

K2

C. g/cm2/year

1880

1895

1910

1925

1940

1955

1970

1985

2000

20151

16

31

46

61

76

91

0,001 0,501 1,001 1,501 2,001 2,501 3,001 3,501

x10

years

depth,cmOK2

N. g/cm2/year

1885

1910

1935

1960

1985

20103

13

23

33

43

53

63

73

83

93

0,02 0,03 0,04 0,05 0,06 0,07

x100

Years

Depth,cmOK2

Cu. g/cm2/year

1885

1905

1925

1945

1965

1985

20053

13

23

33

43

53

63

73

83

0,01 0,06 0,11 0,16 0,21 0,26 0,31 0,36 0,41 0,46 0,51 0,56

x10

yea

rs

Dep

th, c

m O

K2

Zn. g/cm2/year

1885

1910

1935

1960

1985

20103

18

33

48

63

78

93

0,1 0,6 1,1 1,6 2,1

x100

Years

Depth,cmOK2

P.g/cm2/year

1885

1910

1935

1960

1985

20103

18

33

48

63

78

93

100 150 200 250 300

x100

Years

Depth,cmOK2

Sio2. g/cm2/year

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23

KK2: agriculture area Figure 5 shows the distribution of Cu, Zn, N, C and Si flux at this site.

The highest and the lowest values for the Cu flux are 0,08 g/cm2/year and 0,05

g/cm2/year, respectively. There is one extreme value at 0,05 g/cm2/year. The flux for

Zn does not vary so much and the highest and the lowest values are 0,09 g/cm2/year

and 0,12 g/cm2/year.

The flux for N increases, but around 1959 the values start to decrease. The highest

and the lowest values are 11,8 g/cm2/year and 0,26 g/cm2/year, respectively.

The flux for C in general increases exponentially and later decreases. The highest and

the lowest flux are 210 g/cm2/year and 16 g/cm2/year, respectively. The highest and

lowest Si flux are 332 g/cm2/year and 171g/cm2/year, respectively.

Figure 5. The elemental flux Cu, Zn, N, C and Si at site KK2.

1738

1788

1838

1888

1938

198811

19

27

35

43

51

2 27 52 77 102 127 152 177 202

yea

rs

dep

th

,cm

KK

2

C. g/cm2/year

1738

1788

1838

1888

1938

198811

21

31

41

51

0,1 2,1 4,1 6,1 8,1 10,1 12,1

years

dep

th

,cm

K

K2

N. g/cm2/year

1844

1869

1894

1919

1944

196911

16

21

26

31

0,04 0,05 0,06 0,07 0,08 0,09

years

Dep

th

,cm

KK

2

Cu. g/cm2/year

1844

1869

1894

1919

1944

196911

16

21

26

31

0,08 0,09 0,1 0,11 0,12 0,13

Years

Depth,cmKK2

Zn. g/cm2/year

1844

1869

1894

1919

1944

196911

16

21

26

31

130 180 230 280 330 380

years

Depth,cmKK2

Sio2.g/cm2/year

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24

SPK2: agriculture area Figure 6 shows Cu, Zn, N, C and Si flux in the sediment core at the SPK2 site. The

core extends to 1846 AD and is 92 cm deep. At 40 cm, the concentrations of Si, Cu

and Zn are very high. In order to indicate these values in the same graph it should be

noted these values are 4 times higher than what is indicated in the graph.

The flux for Cu increases from 0,02 g/cm2/year to its highest value 0,08 g/cm2/year at

40 cm depth. Flux for Zn does not show much variation except for the sharp increases

at 92 cm depth. The flux for N increased exponentially and there is an extreme value

The highest and the lowest value for N are 1,08 g/cm/year and 0,07 g/cm2/year,

respectively.

In general, the values for C increase but there are some variations. The highest and the

lowest values for C are 16g/cm2/year and 0,9g/cm2/year, respectively. The highest

flux of Si is 353 g/cm2/year where the depth is 40 cm and the lowest value is approx

88 g/cm2/year.

.

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25

Figure 6. Cu, Zn, N, C and Si in the sediment core at the SPK2 site. Note that the values Si, Cu and Zn

are four times higher than what is noted in the graph.

1852

1877

1902

1927

1952

1977

20023

1323334353637383

70 80 90 100 110 120 130 140 150 160

x4

Yea

rs

Depth,cmSPK

2Sio2. g/cm2/year

1852

1877

1902

1927

1952

1977

20023

16

29

42

55

68

81

94

0,01 0,015 0,02 0,025 0,03

x4

Years

Depth,cmSPK

2

Cu. g/cm2/year

1885

1910

1935

1960

1985

20103

23

43

63

83

0,028 0,029 0,03 0,031 0,032

Years

Depth,cmSPK2

x4

Zn. g/cm2/year

1846

1861

1876

1891

1906

1921

1936

1951

1966

1981

1996

20111

16

31

46

61

76

91

0,012 0,212 0,412 0,612 0,812 1,012

Yea

rs

Dep

th,c

m S

PK

2N. g/cm2/year

1846

1866

1886

1906

1926

1946

1966

1986

2006

1

16

31

46

61

76

91

0,01 2,01 4,01 6,01 8,01 10,01 12,01 14,01 16,01

Yea

rs

Dep

th,c

m S

PK

2

C. g/cm2/year

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26

KP1A: agriculture area Figure 7 shows the values of Zn and Si at site KP1A which extends to a depth of 96

cm. The flux for Zn has the highest value 0,007 g/cm2/year and the lowest value is

0,001 g/cm2/year. The highest and the lowest values for Si flux are 21,6 g/cm2/year

and 7,60 g/cm2/year, respectively

Figure 7. Zn and Si flux at site KP1A. As was noted under Limitation, the flux for Si and N in site KP1A are not included because inconclusive rate.

Discussion There are variations in spatial and temporal conditions in elemental flux in the cores.

In addition, there is a distinct change in rural versus urban locations at the coring sites.

These variations are related to land-use changes that have happened in the catchment

and follow expected norms highlighting anthropogenic activities and soil disturbances.

Below we have discussed the overall elemental flux for each site and what we can

infer from such trends in the sediment cores.

187218861900191419281942195619701984199820127

27

47

67

87

6 8 10 12 14 16 18 20 22years

Dep

th

,cm

KP

1A

Sio2. g/cm2/year

1883

1903

1923

1943

1963

1983

20037

22

37

52

67

82

97

0,0001 0,0011 0,0021 0,0031 0,0041 0,0051 0,0061 0,0071 0,0081

Yea

rs

Dep

th,c

m K

P1

A

Zn. g/cm2/year

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27

Zn The flux for Zn was in general higher in the agricultural sites (KK2, SPK2, KP1A)

compared to the urban areas (OK2, DK2). The Zn flux for different sites ranged in the

following order: KK2 (0,01-0,12 g/cm2/year), OK2 (0,06-0,10 g/cm2/year), SPK2

(0,03-0,12 g/cm2/year), KP1A (0,001-0,007 g/cm2/year), DK2 (0,005-0,0065

g/cm2/year). In the agricultural areas (KK2, KP1A, SPK2) the values started to

increase while SPK2 had the same value 0,03 g/cm2/year for an extended time.

During the 1870s the Zn flux in KK2 declined and in the 1930s at KP1A site Zn

declined too. However, for SPK2, during the 20th century the values increased rapidly

from 0,03-0,12g/cm2/year. The flux for Zn at site SPK2 increased around 1904. The

value was four times higher (0,03x4 g/cm2/year). After this extreme deviation, Zn

continued as 0,03 g/cm2/year until 2004. Furthermore, the flux at site KK2 started

from 0,11 g/cm2/year in 1844 and decreased to 0,12 g/cm2/year. The values of KK2

showed a decreasing trend from 1870s to1980s and continued with the annual flux

pegged around 0,09 g/cm2/year.

At site KP1A, from the beginning of 1880s to 1930s, accumulation increased and

ranged from 0,002 g/cm2/year to 0,003g/cm2/year and from 0,003 g/cm2/year to 0,006

g/cm2/year. From 1940s to 1950s, the values started to decrease from 0,002

g/cm2/year to 0,001 g/cm2/year and later on, the values increased again. It increased

from 0,003g/cm2/year to 0,007g/cm2/year and then the value decreased in 2009.

At OK2 and DK2 that are urban areas, the flux differs between each other sites. At the

top of 24 cm in DK2, the values started with a flux of 0,006 g/cm2/year in 1840s and

remained the same until 1930, the values then started to increase in the 1980s. From

24 cm to 56 cm depth in 1500-1800 AD, the accumulations oscillated.

It started from 0,0005g/cm2/year and increased to 0,0028. It further increased to 0,009

g/cm2/year before decreasing to 0,006 g/cm2/year. The variation in accumulation

possibly indicates land use changes from 15th century onwards.

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Furthermore, in OK2 the flux started with 0,07 g/cm2/year and continued to have low

values ca. 0,06 g/cm2/year to 0,1 g/cm2/year except in 1936. Most likely something

happened around this time that made the flux for Zn 10-times higher (∼5,2

g/cm2/year). The variation in accumulation is most likely due to land use changes.

Cu The elemental flux for Cu is high in the agriculture areas (KK2) compared to urban

sites (OK2). However, the flux at site SPK2, which is from an agriculture area was

lower than OK2 and KK2.

The sites ranged in following order: KK2 (0,05-0,08 g/cm2/year), OK2 (0,03-0,06

g/cm2/year) and SPK2 (0,02-0,03 g/cm2/year). The flux between sites KK2 and OK2

did not differ that much. Even though SPK2 and KK2 are from a remote site, and

SPK2 is a more remote site than KK2, there are differences between the flux.

At site SPK2, the flux for Cu values started at 0,02 g/cm2/year and this value was

more or less steady until 1898. However, during the 20th century, there was an

enormous change because the value was four times higher. The flux varied down core

from 0,02-0,03 g/cm2/year in 1852 to 1898 and from 1910 to 2004.

The flux at site KK2 varied more than SPK2. The flux was 0,07 g/cm2/year in the

1840s and increased to 0,08 g/cm2/year during the period 1871 to 1907. However, the

flux decreased to 0,05 g/cm2/year and near the top of core, it varied between 0,06 and

0,07 g/cm2/year from 1969 to 1982.

The urban area at site OK2 oscillated with the flux more than the other two sites. The

flux started with a value of 0,04 g/cm2/year in the 1880s, and it increased to 0,06

g/cm2/year and then decreased to 0,05g/cm2/year. The flux again increased in 1926.

The flux kept oscillating from 0,04 g/cm2/year to 2,9 g/cm2/year, 0,04 g/cm2/year to

0,05 g/cm2/year in 1964 and then it decreased again to 0,04 g/cm2/year.

Afterwards, it increased to 0,05 g/cm2/year from 1983 to 2009. The flux increased

dramatically at 40 cm depth.

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Lalah et al (2010) studied Lake Victoria sediment in two districts, Kisumu and Busia.

They found e.g. high values for Cu and Zn in Lake Victoria. The high values for Cu

and Zn were attributed to the anthropogenic sources (Lalah et al. 2010). The average

values for Zn and Cu in their study were Cu (26.3–80.7%) and Zn (41.5–93.8%).

These values were much higher compared to what was found in this study at the

different sites Kisumu (DK2 and OK2), Busia (SPK2), Siaya (KK2) and Kapsabet

(KP1A).

In their study, they don’t have the opportunity to report results in flux as we do, so

they reported in percentage. We had the choice to choose to report our values in

fluxes and in percentage. The values in percentage of our Cu and Zn for the six sites

were: DK2 (Zn, 0,005–0,02%), SPK2 (Cu, 0,006–0,008 and Zn 0,007–0,01%), KP1A

(Cu, 0,004–0,011% and Zn, 0,002–0,01%), HK2 (Cu, 0,003–0,02% and Zn, 0,006–

0,02%) and KK2 (Cu, 0,06–0,01% and Zn, 0,011–0,015%) and OK2 (Zn, 0,01-0,02

% and (Cu, 0,008%-0,011 %).

The low values for Cu and Zn in these sediments compared to Lalah et al (2010) in

Lake Victoria sediments implies no anthropogenic influences. There are certain

variations in the flux for these elements and these are possibly related to historical

events that had an affect (Figs. 3-7).

Even though the values of Zn and Cu flux were small and could not be related to

anthropogenic influences connected to eutrophication as suggested by Lalah et al

(2010), there were some historical changes in the catchment that probably had an

impact on elemental concentrations at site SPK2 and OK2. The flux of these sites may

be linked to historical changes because, in 1900s according to (Hecky, 2010), when

the railroad started from Kisumu went all the way to Kampala, there were some peak

values at site SPK2 in 1904 and OK2 in 1936 for Cu and Zn (Figs.3 and 4).

Lalah et al (2010) indicated, if there is high in percentage of organic matter in

sediments, it could significantly contribute to the bioavailability of heavy metals in

these sediments. This means organic matter in sediments will leads to increase of

metal adsorption capability in the sediments (Lalah et al.2010; Mwamburi, 2013).

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A study by Mwamburi and Oloo (1994) on concentration and distribution of metals in

sediments, surface and bottom water in Lake Victoria found Zn to be at higher levels

in sediments near Kisumu and Homa Bay compared to other surrounding areas in the

lake. However, the authors stated that this indicates the influence of metals pollution

from activities in surrounding towns e.g. in harbor, vehicles using leaded fuel and

paints, effluents from industries and municipal wastes (Mwamburi and Oloo, 1994).

N N flux in sediments was the highest at the agriculture sites compared to the other sites

i.e., OK2, DK2 and SPK2. The N flux at the different sites were as follows: KK2

(0,26-11,8 g/cm2/year), OK2 (0,42-3,54 g/cm2/year), DK2 (0,06-1,2 g/cm2/year) and

SPK2 (0,07-1.00 g/cm2/year).

The values for the accumulation flux at site KK2 showed an exponential increase

even though they oscillated. The N flux at site KK2 started at 1,39 g/cm2/year and

then it decreased. The variation in N flux encountered in the following order: 1.39-1.3,

1.56-1.64, 2.42-3.83, 2.87-3.12, 3.9-5.8, 5.6-6.2 and 6.07-7.02, 8.68-10.78, 11.86-

10.98, 0,26 g/cm2/year from 1730s to 1980s.

Flux values at the site in Kisumu (OK2) range from > 0,50− >0,8 g/cm2/year during

the periods 1880s - 1907, 1912-1933 and 1938- 1991. Except this, there were two

extreme values, one at depth 40 cm in 1936 and another at 65 cm in 1910. At 40cm

depth, the value was 10-times higher (3,50 x 10 g/cm2/year) and at 65cm, the value

was 3,42 g/cm2/year. After the end of 1990s, the flux started to increase from 0,89

g/cm2/year to 1,00 g/cm2/year. The flux remained mostly steady, even if it increased

slowly. The flux ranged from 1,16-1,21 g/cm2/year and 1,50-1,32 g/cm2/year.

Kisumu (DK2) site did not show a distinct increasing trend of the accumulation flux

as in KK2 and OK2.

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The values mostly oscillated within 0,12-0,16 g/cm2/year starting from the year 1531

and extending up to the 1930s. The increase in flux of sedimentary N occurs in the

bottom layer from 42 cm to 56 cm from 1609 to 1531, N ranged from 0.12-0.14

g/cm2/year and 0.16-0.17 g/cm2/year. From the 1620s -1710, the values decreased

from 0,14 g/cm2/year to 0,1.0 g/cm2/year and then it started to increase again to 0,14

g/cm2/year. The next 100 years to the 18th century, the flux oscillated from 0,13-0,15

g/cm2/year. After the following year, the values were 0,13 g/cm2/year from 1840 to

1860. Near the top of the core, the flux from 1912 to 1985 oscillated from 0.16-0.06

g/cm2/year and 1.19-0.25 g/cm2/year.

The N-flux at SPK2 increased steadily; it started in 1846 from 0,07 g/cm2/year to 1,08

g/cm2/year during the 20th century. From 1800s to beginning of 1900s, N flux values

oscillated exponentially increasing from 0,07 g/cm2/year to approximately >0,10

g/cm2/year from 1846 to 1880 and from 1880s to 1890, the N-flux increased from

>0,10 to >0,2 g/cm2/year and furthermore, the flux in 1901 started from >0,30

g/cm2/year to later on oscillate within ( >0,30 to >1,00 in 1904, >0,20 to >0,30 in

1913, >0,30 to >0,40 in 1940s, >0,40 to >0,50 in 1967 and >0,50 to >0,80, >0,10 to

1,08 g/cm2/year in 1967 to 2011). In 1904, there was a peak of 1,08 g/cm2/year,

respectively.

All N flux values at the four sites, except DK2 had the same strong pattern, seemed to

have a clear correlation to the historical changes in the catchment (Fig. 3-6 compare

with Fig.1).

According to historical changes in the catchment when the railroad started from

Kisumu in 1900s and went to Kampala 1932, there were some peaks in N-flux values

at the sites and they were; SPK2 in 1904, OK2 in 1910 and 1936, DK2 in 1935 to

1960, and KK2 in 1959.

When the population, agriculture, productivity and livestock increased, these caused

an increased pressure on land and ecosystems. Furthermore, the forest clearance

before 1950s may influence lake sediment quality (Hecky, 2010), because

at site DK2 in Kisumu from 1935 to 1960, the N flux values increased exponentially

from 0,06 to 0,25 g/cm2/year.

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During 1926 and 1959 at site KK2, the N flux values increased exponentially from

>8,60 to >11,8 g/cm2/year, In the other sites (SPK2 and OK2) the flux increased but

was not rapid like the other sites. Except human impact, there is also natural events

that can affect sediments like poor water ventilation, oxygen depletion, water

temperature and pH (Wetzel, 2001; Yang, Z. 2015).

Another factor that can have had an affect on sediments are the three years period of

heavy rainfall in 1960-64 (Bootsma, Hecky & Odada, 2006; Hecky, 2010) when the

water containing nutrients drained in to the lake. According to this, all N-flux values

increase steadily and have some peaks at site KK2 at the end of 1950s (>11,8

g/cm2/year) and at DK2 in 1960 (>1 g/cm2/year).

C The flux values for C were highest near agriculture areas at site KK2. In fact, the flux

values were higher than, compared to the other sites, SPK2, OK2 and DK2. The flux

values between the sites ranged from: KK2 (16-210 g/cm2/year, agricultural area),

OK2 (6-56g/cm2/year, urban area), SPK2 (0,12-16 g/cm2/year, agricultural area) and

DK2 (0,75-3,40 g/cm2/year, urban area).

The site KK2 had the highest flux and accumulation between the different sites. At 56

cm, the value started at 19,8 g/cm2/year around 1738 and increased steadily unto 1755

with an accumulation of, approximately 23,0 g/cm2/year. Furthermore, after the 1750s

the accumulation started to decrease again in the 1770s. However, it did not last that

long before it started to increase around 1783 (30 g/cm2/year). During the 1790, 1800

and 1820s, the values oscillated from (~52 to 36 and ~42 to 54 g/cm2/year). The

accumulation kept on increasing steadily in the 1830s to the end of 1950s with a

varying range (>74,0 -210 g/cm2/year). After the two following years 1976 and 1982

from 12-14 cm depth in the sediment core, the values decreased from (160 – 88,0

g/cm2/year). A sign of land use changes can be ascertained from the 1730s to 1840s.

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The accumulation at site OK2 did not vary so much and changed from 8 - 12

g/cm2/year). During the beginning and the end of 1880s the flux was from 9.0 - 11.0

g/cm2/year and in the 20th century, the accumulation increased and ranged from 12,8

g/cm2/year to 13,7 g/cm2/year. However, the flux increased from 12,2 g/cm2/year to a

high amount at 49,4 g/cm2/year. C values during the 20th century were higher than the

1990s, and varied from 12,0 g/cm2/year to 13,0 g/cm2/year. However, in 1910, there

was a sharp rise in accumulation which compared to the general accumulation flux

during other periods was approximately 50 g/cm2/year.

After these sharp changes, the flux decreased rapidly again and oscillated within (8,0-

10,0 g/cm2/year) from year 1912 to 1933. At 40 cm i.e. around 1936, there was an

increase in accumulation (56,0 g/cm2/year). During the rest of 1930s, accumulation

decreased to 7,58 g/cm2/year and in 1940s to early 1960s, the values were (~6-12

g/cm2/year). The flux gradually increased to (10,0- 12,0 g/cm2/year) from year 1969

to the end of 1990s. The accumulation of C kept increasing steadily in the 21th century

(14,0-17,0 g/cm2/year).

Busia (SPK2) had the third highest accumulation rather than increased exponentially,

in general from bottom to the top of the core the values changed from 1,00 g/cm2/year

to 13,0 g/cm2/year. The increases in flux could be a sign of anthropogenic activities.

From 1846 to 1858, the flux varied from 0,90-1,11 g/cm2/year. It decreased in 1868 to

0,12 g/cm2/year. Later it started to increase again around 1871 to 1886, and stabilized

around 2,00 g/cm2/year. The accumulation of C increased exponentially with a range

from 2,00 -13,0 g/cm2/year during the period 1886-2011.

In DK2, C flux was the lowest between all the four sites. At the top, around 26 cm,

the accumulations during 1819 to 1985 varied from 1,80−3,40 g/cm2/year). Rest of

the 56 cm in this core extending from 1531 to 1793 were events in lake that do not

connected to human activities. The C flux from various sampling locations in Kenya

varies from 0,01-210 g/cm2/year. The values are highest at SPK2 and KK2 that are

agriculture areas. Both sites have similar pattern as far as the historical changes in the

catchment and therefore show similar depositional histories (Figs. 1, 3 and 6).

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The increase in C flux during the 1900s could have been caused by the start of the

railroad construction around Kisumu which lead to increased soil disturbance and

urbanization. The peak for high C flux from the different sites are as follows: 1) KK2

(1959, 210 g/cm2/year) and started to increase from 1907 that was around 121

g/cm2/year; 2) SPK2 (1904, 16,0 g/cm2/year); 3) DK2 (from 1935 to 1985, 0,75-3,4

g/cm2/year) and 4) OK2 (1936, 56 g/cm2/year) which started to increase around 1910.

Furthermore, the agricultural and extensive forest clearance according to Hecky (2010)

may also have had an additional impact that increased the flux.

Additional input from traffic and vehicular runoff since the 1950s (Awange and

Obera, 2007) also had an affect on the C flux variations.

Mwamburi (2013) reported the metal concentrations in water, sediments and biota in

Lakes Victoria and Naivasha. They reported that Lake Naivasha had lower

concentration of organic matter than Lake Victoria sediments and ranged from 0.4±

35.7%. The total organic matter in their study from Lake Victoria ranged from 1.3%

to 38% which is comparable with this study that also had nearly exactly the same

values. Mwamburi (2013) stated that organic matter ranging from 10-38% in offshore

sediments, reflected the high lake productivity as a consequence of anthropogenic

inputs.

The values of OC from KP1A, KK2 and SPK2 showed higher values in agriculture

areas compared to the urban area. The urban sites Kisumu (DK2 and OK2) and the

agriculture site Busia (SPK2) had low values of C in sediments during the early 19th

century when these area had fewer farmlands.

The C values changed from 0,30 to 3,64%. In the early 1900s, (Fig. 8), the railroad

arrived in Kisumu and thereafter, during the 20th century, the values for carbon flux at

site OK2 and SPK2 increased exponentially implying a causal link. In contrast, at

DK2 the values were steady and varied between 1,0 – 3,0%. However, later on at site

DK2, the C levels started to increase in 1960s. At site DK2 and OK2 in 1985 and

2014, the C values were 6,00% and 3,75%, respectively. In 2011 at site SPK2, the

value was 3,75%. For all these sites, the values seemed to keep increasing indicating

the role of human activities on elemental flux.

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P A definite change in P flux, only occurred in the OK2 sediment core that is an urban

area. In this case the variation was from 0,28-68.0 g/cm2/year. The sediment flux

started with the value 0,84 g/cm2/year in 1885 and increased to >1,10 g/cm2/year in

the 20th century. Then it started to decrease slightly. In 1936, the accumulation

increased rapidly (0,98-0,68 x 100 g/cm2/year) and afterwards the flux declined

rapidly again. During the period 1940-60, the value started to oscillate a little within

(1,00-1,24 g/cm2/year) and in the 1970s the flux decreased to 0,28 g/cm2/year.

Furthermore, after 1970s the value mostly increased until the 21th century and after

that, it started to decrease again.

There are some changes in the P flux values that seems to be related to historical

changes in the catchment and one of these events is when the railroad arrived in

Kisumu during the early 1900s (Brown, 2002). Around this time the P flux increases

from > 0,80 g/cm2/year in 1885 and >1,0 g/cm2/year in 1907. Other events in the

catchment are the rise agriculture and forest clearance before 1950s (Hecky, 2010)

which can explain the peak for P flux (0,98-68g/cm2/year) in 1936 The heavy rainfalls

around 1962-64 had a little noticeable impact on P flux (Fig. 4).

Another explanation of P flux increasing from 1974 onwards from (0,28 g/cm2/year to

1,58 g/cm2/year) can be due to the internal P-loading from hypolimnetic anoxia

during the 1970s (Hecky, 2010). Vollenweider (1968) estimated that the general

permissible P-loading rate for lakes is 0.07 g/ m-2 /yr-1 (7x10-6g/cm2/yr) and this could

be used as a benchmark. These P flux values ranged from 0,28 g/cm2/year to 1,58

g/cm2/year, except the peak of (68 g/cm2/year), compare to what Vollenweider (1968)

estimated as a benchmark were much higher.

Gikuma-Njuru et al. (2009) indicated that P sedimentation rate is higher than P

release rate in most lacustrine systems (Gikuma-Njuru, 2013). The high concentration

of P at OK2 site, which is from an urban area, compare to Vollenweider (1968) can be

explained based on this argument.

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However, if there are high values, this can be related to chemical weathering of

erosion caused by land use changes in the catchment (Gikuma-Njuru, 2013) and from

external inputs of phosphorus by fluvial processes (Chen et al. 2015).

The high P concentration that was found in Lake Victoria sediment cores, in the

catchment and in the open waters, has been linked to chemical weathering due to land

use changes in the catchment, and the increased P input that happened in the last few

decades (Gikuma-Njuru, 2013).

It is also important to keep in mind that the influences from river input of

P, into the gulf, has a direct affect on P concentration in bottom sediments. Gikuma-

Njuru et al. (2013) referred to the Management Project (LVEMP 2005b) that

suggested the release of P rate in sediments was approximately 1.73 mg/m2/day

(6,3x10-5 g/cm2/year) in Nyanza and they conducted that the sediment in the gulf

could be a net P sink. Nonetheless, the P values at site OK2 ranged from 0,28

g/cm2/year to 68.0 g/cm2/year which are much higher in comparison to other sites.

Consistent with this change during the 1960s, P concentration and primary production

increased in the lake (Cumming et al. 2009).

Si The flux for Si represents both low and high values in urban areas (OK2, DK2)

compared to agricultural sites (KP1A, KK2, SPK2). The highest flux was, 127-11978

g/cm2/year at site OK2 and the lowest flux was, 4,5-13,0 g/cm2/year at site DK2.

Flux from the different sites ranged in the following order: OK2 (127-11978

g/cm2/year), SPK2 (88-353 g/cm2/year), KK2 (171-332 g/cm2/year), KP1A (7,6-21,6

g/cm2/year) and DK2 (4,50-13,9 g/cm2/year).

The flux at site SPK2 oscillated most in the rural areas. It started from 1850s where

the flux was approximately 135 g/cm2/year and decreased to 88,7 g/cm2/year. Later

on, the flux increased exponentially to 144 g/cm2/year until 1892.

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Then the value started to decrease to 139 g/cm2/year, but later on increased to 353

g/cm2/year in the 20th century. From the period 1910-1960, the accumulations varied

(119 – 160 g/cm2/year) and later decreased.

At KK2, the flux started with the highest value around the 1870s (332 g/cm2/year) and

decreased steadily from 282-135 g/cm2/year and increased to 235 g/cm2/year near the

top (12 cm).

At site KP1A, the Si flux was one of the lowest values, approximately 8 g/cm2/year

during the 1870s that increased. The values increased until 1940s, and was 21

g/cm2/year before it decreased. In the upper 56 cm interval of the core, the Si flux

varied from 11,0-21,0 g/cm2/year from1943-61. Near the top of the core the flux

varied from17 g/cm2/year to >15 g/cm2/year and later decreased to 14,7 g/cm2/year.

At the urban site OK2, the flux was 267 g/cm2/year but afterwards the value

decreased. During the 1930s at 40 cm depth, there was a flux of 11978 g/cm2/year and

then it started to decrease again. At the top of the 30 cm interval, the Si flux varied

from 120-200 g/cm2/year and ended at 158 g/cm2/year in 2009.

At the other urban site DK2, which is closer to urban settlements, the Si flux is low at

the start but gradually increased over the years. The flux changed from the 1500s

to1840 ranging from 4.00-10.0 g/cm2/year. This is mainly due to land use changes.

From the 1840s-1980s, the flux increased from >10 g/cm2/year to 14 g/cm2/year.

From 1980 onwards the Si flux continued to increase due to varying natural causes.

None of the Si flux coming from the five sites, see figures 3 to 7, have same trend as

the historical changes in the catchment. Therefore, it is more likely that variations in

the Si flux are caused by natural factors. Furthermore, change in Si content in the

water column depends on other factors besides anthropogenic changes such as

temperature, degradation/erosion of rocks and minerals, and influent water derived

from surface streams and rivers. Si is a component derived from rocks, minerals and

degradation of aluminosilicate minerals (Wetzel, 2001).

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The increase and decrease of Si flux in sediments from the sites seems to be caused

by natural events due to hydrological changes and erosion/weathering rather than

anthropogenic activities. In a study focusing on Lake Victoria surface-sediment cores

that came from six offshore stations in 1995, the Si concentrations were around 5% of

dry mass and it is considered low. Brown et al (2002) indicated that it reflected the

stable diatom production in the lake before the impact of increase in human

population (Brown et al. 2002).

Furthermore, diatoms require Si for its growth (Kamatani & Oku, 2000) and therefore,

if there is lot of dissolved Si in the water, they will be taken up by diatoms and cause

eutrophication. Moreover, if there has been a high degradation rate of diatoms and

organic compounds, Si will be released from the upper layer of soil into the water

column (Conley et al, 2005). The release of silica from sediments will also depend on

temperature (Wetzel, 2001).

According to the five inshore sites, compared to the study by Brown et al (2002), the

concentrations for Si were higher, and varied from (8,00-25,0%), (10,0-29,0%), (1-

46,0%), (24,0-51,0%) and (26,0-51,0%). During the late 20th, century the Si

concentration declined by 80% (Cumming et al. 2009), but the Si concentrations for

the four sites (KP1A, SPK2, OK2 and DK2) changed a little except site KK2 during

(1969-1982). In site KK2, Si increased by 73%. Because diatoms require Si for their

growth, variations in Si concentrations can maybe explained by availability of

diatoms, constant inflow from rivers or weathering of marine sediments (Kamatani &

Oku, 2000).

Do metal fluxes influence eutrophication? The flux for Cu and Zn could not be linked to anthropogenic sources according to

Lalah et al (2010) that studied Kisumu and Busia. There were however small changes

in the flux when the railroad started as noted in this study.

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The relatively low content of N in the sediments in this study, may be explained based

on the sediment characteristics and bonds. The sediments indicate oxidized microzone

at the sediment at the water interface. This will reduce the adsorptive capacity of

sediments for NH4 – N. The sediment will however release N from NH4 under

anaerobic condition (Wetzel, 2001). Even if the sediments do not show high values of

N, there is a large amount of N inflow from the atmosphere, which is suggested by

Kirimire et al (2006) that came from biomass burning from the catchment. Kirimire et

al (2006) also stated that deforestation, agricultural practices and grazing have

contributed to soil erosion.

The OC flux seems to reflect the historical changes in the catchment due to human

activities and may influence the eutrophication in Lake Victoria. This is based on the

peak OC values relate to the historical changes in the catchment and eutrophication in

the lake (Brown et al. 2002; Kirimire et al., 2006). However, all the sites do not show

the same historical pattern in increased flux as Brown et al (2002) except the

agricultural areas KK2 and SPK2. This can be due to the agricultural practices

(Brown et al., 2002; Kirimire et al., 2006) that happened in the catchment.

P flux in OK2 showed high values according to Vollenweider (1968) and Gikuma-

Njuru et al. (2013) that referred to the management Project (LVEMP 2005b) can be

the explanation to these values. Furthermore, these values reflect the historical

changes in the catchment and Gikuma-Njuru et al (2013) suggested this can be due to

erosion caused by land use changes in the catchment, and from external inputs.

Kirimire et al. (2006) said that the combined nutrient load from all sources has

contributed to building up the P and N content in Lake Victoria. The authors stated

that the extent of eutrophication in Lake Victoria is more dependent on the

concentration of P and N derived mainly from use of fertilizers in the catchment P

input from rivers into the Gulf of Nyanza and had a direct affect on P concentration in

bottom sediments. The authors also proposed there is a substantial input of

atmospheric P input into the lake to the tune of 15,00-24,400 tP/yr derived mainly

from biomass combustion. However, with these few P flux values, any conclusions

can not be absolutely drawn to say that the P flux influence on eutrophication in LVB.

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But, monitoring and research on water quality may give a better understanding about

P contribution and influence on eutrophication.

In comparison with the study by Brown et al. (2002) the Si values in percentage in

this study were high. These high flux values are most likely due to the natural causes

involving weathering process of rocks and minerals and inputs from rivers which adds

Si. Because Si is an element coming from natural sources and its concentration in

water is pH and temperature dependent, the Si flux is most likely linked to natural

processes that influence eutrophication.

Conclusions Six elements have been analysed and correlated with historical changes in the

catchment to see if they influenced the eutrophication in Lake Victoria. The Cu, Zn

and N fluxes implies to historical land use changes in the catchment, but there were

no sign or indications of historical anthropogenic influences coming from the

catchment that can influence the eutrophication in the lake. The Si flux variations can

most likely be explained by the natural historical events and factors within the lake.

The P flux values reflect the historical changes in the catchment and seems to be high

based on a study that exist and affected by external input. But there are too few P flux

values to state that the values have an influence on eutrophication in LVB. Amongst

the different elements analysed C seems to be most influenced by land-use changes in

the catchment and shows a dramatic rise related to the cultural eutrophication of lake

(urbanization, land-use change, deforestation and railroad construction).

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Validation and reliability To get a better representative picture from different sites regarding the elemental flux

from the catchment, more sediment cores should be taken at same place and also from

other urban and agriculture areas. Furthermore, to get better representative results of

the elemental values the XRF scans should have been in duplicate since XRF

measurements can show lot of variability.

Further study A recommendation for further study is to look at the grain size because it plays an

important role in distribution of metals. More studies need to be done on sediment

characteristic because it acts like a sink and source for heavy metals in the lake.

Reassessment of water quality with elemental flux would give a better results and

localisation of point source inputs coming from the anthropogenic activities leading to

the eutrophication problem in the lake.

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