Dissolved Organic Carbon, Turbidity and Nutrients in Lake

Dissolved Organic Carbon, Turbidity and Nutrients in Lake Viken History and a Snapshot of Sub-catchment ... At high flows water tends to ... reaches R...

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Dissolved Organic Carbon, Turbidity and Nutrients in Lake Viken History and a Snapshot of Sub-catchment contributions

Peter Kloss Degree project in biology, Master of science (2 years), 2014 Examensarbete i biologi 30 hp till masterexamen, 2014 Biology Education Centre Supervisor: Lars Tranvik External opponent: Jovana Kokic

Abstract Lake Viken, situated in mid south Sweden, in the county of Västra Götaland, has in recent years become increasingly turbid and brownish, according to people living in the area. The question was raised whether a ongoing drainage of a peat-bog in the catchment area was contributing to the deterioration of the water quality. The main aims of this work were: •

Investigate how the water quality has changed over time by compiling historic data.



Map the lake´s sub-catchments and in the water from these measure concentrations and transported amounts of substances, e.g. dissolved organic carbon (DOC) and nutrients.



Investigate possible correlations between land-types in the sub-catchments and concentrations.



Compare water chemistry in drainage from the drained bog and a natural bog, and finally, from the results and former studies discuss which impact the drained bog may have on Lake Viken.

The most obvious changes in water quality in Lake Viken, during 1965- 2012 were increased pH and DOC-levels and decreased concentration of total phosphorus . Precipitation in the area increased during the time period and varied together with absorbance. Turbidity showed no trend over time but perhaps it has been a change in what causes it. It could have been a shift from phytoplankton to turbidity caused by terrestrial and sediment originated particles. High proportion of mire and low altitudes in the sub-catchments seemed the most important factors to explain high DOC-levels in run-off water, while phosphorus was linked to proportion of agricultural land. Measurement of suspended matter has to be conducted continuously over a long period in order to give a true picture. The comparison between the drained bog and the natural bog showed that water from the drained bog contained more DOC, suspended materials and nutrients. The drainage of the bog may have increased the total inflow to Lake Viken by about 2%. The contribution of suspended material could be of greater importance.

Sammanfattning Folk boende runt sjön Viken, belägen i Västra Götaland, har de senaste åren noterat att dess vatten blivit allt grumligare. Man undrade huruvida en då pågående utdikning av en mosse i avrinningsområdet bidrog till den försämrade vattenkvalitén. Detta arbetes syfte var att undersöka hur vattenkvalitén har förändrats genom tiden genom att sammanställa historisk data, kartlägga sjöns delavrinningsområden och i vatten från dessa områden mäta koncentrationer och transporter av olika ämnen som t ex löst organiskt kol och fosfor, påvisa korrelationer mellan marktyper och koncentationer samt att göra en jämförelse mellan den dikade mossen och en naturlig mosse för att slutligen, med hjälp av tidigare studier, dra slutsatser kring den dränerade mossens påverkan på sjön Viken. Resultaten visar att halten löst organiskt kol (DOC) och pH-värdet i Viken har ökat över en längre tid och samtidigt har fosforhalten minskat. Nederbörden i området ökade under tidsperioden och varierade samstämmigt med absorbansen. Turbiditeten uppvisade ingen trend över tiden men möjligen kan det ha skett en förändring av vad som är orsaken. Vattenkvalitén från de olika delavrinningsområdena skiljer sig mycket. Koncentrationer av DOC korrelerade starkast med medelaltituden i avrinningsområdet och med andelen myrmark, medan fosfor kopplades till jordbruksmark. Mätning av turbiditet och suspenderat material måste ske kontinuerligt över en längre tid för att ge en representativ bild. Jämförelsen mellan den dikade mossen och den naturliga visade att högre halter av DOC, suspenderat material och näringsämnen kom från den dikade mossen. Dikningen av mossen kan ha ökat tillflödet av DOC med ca 2% till hela sjön men tillskottet av suspenderat material kan vara av större betydelse.

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Table of Contents 1. Introduction................................................................................................................3 aims...............................................................................................................................4 2. Methods.....................................................................................................................4 2.1. Historic compilation of Lake Viken.........................................................................4 2.2 Snapshot of inflows and catchment analysis..........................................................5 2.2.1 Sampling and analysis.........................................................................................5 2.2.2 Catchment analysis..............................................................................................5 2.2.3 Loads....................................................................................................................6 2.2.4 In-lake loss...........................................................................................................6 2.2.5Gradient in Lake Viken..........................................................................................6 2.3 Comparison of a Natural Bog and a Drained Bog...................................................6 3. Results.......................................................................................................................7 3.1 Historic Compilation of Lake Viken..........................................................................7 3.2 Snapshot of Inflows and Catchment Analysis.........................................................8 3.2.1 Gradient in Lake Viken.......................................................................................10 3.2.2 Loads..................................................................................................................10 3.2.3 Loss....................................................................................................................11 3.3 Comparison of a natural bog and a drained bog...................................................11 4. Discussion............................................................................................................... 12 4.1 History....................................................................................................................12 4.1.1 DOC....................................................................................................................12 4.1.2 Turbidity..............................................................................................................13 4.2 Snapshot -study.....................................................................................................14 4.2.1 Gradient in Lake Viken.......................................................................................14 4.2.2 Loads..................................................................................................................14 4.2.3 In-lake loss.........................................................................................................14 4.2.4 Correlations........................................................................................................14 4.3 Importance of the drained bog Ryholms Stormosse.............................................14 4.4 Conclusions and Outlook......................................................................................16 5. Acknowledgments....................................................................................................16 References..................................................................................................................17 Appendix 1: Historic data on water chemistry from the channel of Forsvik and precipitation in Skara..................................................................................................................................................... 20 Appendix 2: Results from sampling of rivers and from Lake Viken and the bog Myrhulta mosse....20

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1. Introduction Lake Viken, situated in mid south Sweden, in the county of Västra Götaland (fig.1), has in recent years become increasingly turbid and brownish, according to the water owners and conservation association of Lake Viken (Vikens fiskevårdsområdesförening 2012). The direct cause for brown water is in most cases humic dissolved organic carbon (DOC) of terrestrial origin (Watts et al. 2001) but could also be iron or manganese (Kritzberg & Ekström 2011). Change in DOC concentration affects the lake ecosystem in several ways. Being a substrate for bacteria (De Lange et al. 2003) DOC plays an important role in the food web structure in lakes (Jansson et al. 2007). DOC reduces penetration of solar ultraviolet (Morris et al. 1995) and photosynthetically available radiation (Karlsson et al. 2009), which in turn affects organisms in the lake. There is a trend for several decades in Europe and North America that lakes become browner (Worrall & Burt 2007, Freeman et al 2001). Proposed explanations for this trend are:

Figure 1: Position of lake Viken between the two largest lakes of Sweden, lake Vänern and lake Vättern. Made with free vector and raster map data from naturalearthdata.com.

Higher temperatures through climate change may increase the net primary production as well as degradation of organic matter and consequently, as DOC is a product of decomposition, the load of DOC to lakes (Jansson et al. 2008, Freeman et al. 2001, Worrall et al. 2003). However, temperature alone is unlikely to explain changes in DOC fluxes or concentrations (Tranvik & Jansson 2002, Worrall et al 2004). Production, flux and decomposition of DOC are also linked to hydrology. If warmer and dryer climate results in more oxygenated soils, in which decomposition (DOCproduction) speeds up, the DOC concentrations in streams increase. Lower flows, however, may transport less amounts (though more concentrated) of DOC where longer retention time in lakes means more time for degradation processes in lakes and thus lower DOC-levels. In northern Europe precipitation is thought to increase (SMHI 2013), and also wash out more DOC from the catchments (Hongve 2004, Arvola et al. 2004). At high flows water tends to take a more shallow way through the soils, where the content of DOC is high, and hence high amounts of DOC are flushed into streams (McDowell and Likens 1988).

Humic organic matter is less soluble at lower pH. Accordingly, the recovery from acidification in recent decades, higher pH has been proposed to enhance the solubility of DOC and its transport to streams and lakes. (Monteith et al. 2007). The higher solubility of more negatively charged humic molecules also make them less prone to form aggregates (flocculation) that could leave the water column through sedimentation (Gerritsen and Bradley 1987, von Wachenfeldt & Tranvik 2008). Changes in land-use may affect the export of DOC from soils. Drainage of blanket bogs and peat covered catchments have been shown to increase the release of DOC (Conway & Millar 1960, Mitchell and McDonald 1992, Holden et al. 2004, Mitchell and McDonald1995) and also deforestation could have the same effect (Neal et al. 1998, Schelker et al. 2011, Laudon 3

et al. 2009, Nieminen 2004). Nitrogen fertilization by atmospheric NOx deposition may enhance the production of organic matter and consequently accelerate the DOC production in catchments (Matson et al. 2002). Turbidity is caused by particles, either of autochtonous origin, i.e. plankton and resuspended material from the sediment, or of allochtonous origin through erosion in the catchment. Run off water from peat cutting sites are known to have higher turbidity than the run off from undisturbed peatlands (Pavey et al. 2007). The Water Owners and Conservation Association of Lake Viken (Vikens fiskevårdsområdesförening 2012) has expressed concerns about the impact on the water quality of a recent initiated peat mining area. A relationship has been seen between wetland cover and stream DOC-levels (Eckhardt & Moore 1990). Hope et al. (1997) found a significant correlation between DOC-levels and percentage of peat cover and also with altitude. It is interesting to investigate this type of relationships since they may help to explain differences between sub-catchments of lake Viken. This project aims to : 1. Map the history of Lake Viken's water chemistry by using data from previous years in order to verify whether there is a trend in water quality and if Lake Viken becomes browner and/or more turbid. 2. Investigate the importance of a majority of the inlets to Lake Viken when it comes to transport of DOC, particles and nutrients, and to put them in relation to each other. 3. Investigate signs on in-lake processing of carbon, suspended material and nutrients. 4. Analyse whether there are connections between different land types and elevation in the catchment and the chemistry of the drained water. 5. Compare water chemistry in drainage from a recently drained bog and a natural bog, to shed light on the potential effect on turbidity and DOC of ditching bogs. 6. From the results and other studies discuss which impact the drained bog in the catchment may have on Lake Viken.

2. Methods 2.1. Historic compilation of Lake Viken Data on water chemistry was provided by the Swedish University of Agricultural Sciences (SLU 2013). As data from the middle of Viken only goes back to 1994 data from the main outlet, Forsvik Channel, were used. Data from the outlet Forsvik Channel is a good proxy of the processes in the lake and the water quality should be very similar. Precipitation data comes from Swedish Metrological and Hydrological Institute (SMHI 2013). Annual meanvalues for chemical parameters and total annual amount of precipitation were calculated. Correlations between parameters and patterns over time where investigated by plotting parameters on the time line and using principal component analysis (PCA) which is a multi variable analysis.

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2.2 Snapshot of inflows and catchment analysis 2.2.1 Sampling and analysis During one day (22/11 2012) the cross section area and stream velocity of a majority of all inlets (fig.2) to Lake Viken were measured. Stream velocity was measured using a flow probe that sends the water velocity data to a digital readout display in m/s. The next day, I collected 5 litres of water from each inlet and a duplicate fraction from each sample was filtered through pre-combusted and preweighted Whatman GF/F filters. Filters were dried and then stored in a desiccator to prevent moisture uptake until secondary weighing. Change in mass of filters was used to calculate the amount of suspended matter. Samples Figure 2: Lake Viken, sample points and sub-catchments. The main were also taken from the major outlet goes via Forsvik. Ryholms stormosse, the drained bog, is located outlet from the drained bog, south of Lake Viken. In this map the sample point Spetsbolet includes both the samplepoint upstream the outlet from the bog and downstream. Ryholms stormosse at Spetsbolet, and also upstream The source for the map is vector-format map of terrain from Swedish Surveying Authority. The sub-catchments are generated by the GRASSand downstream the point module r.watershed. ©Lantmäteriet Gävle (2010): Permission I where the drained water from 2010/0058. bog Ryholms stormosse reaches River Örlan. No or very little precipitation had fallen in recent weeks or during the days of sampling. Water was analysed for absorbance (water colour), which is a proxy for DOC, by using spectrophotometric colour determination of filtered water at 436nm (A436), total phosphorous (tot-P) (Menzel 1965), Molybdate reactive phosphorus (MRP) (Murphy 1962), total nitrogen (tot-N) (Crumpton et al 1992), ammonium-N (Berthelot 1859), nitrite-N, nitrate-N (SS-EN ISO 13395), turbidity, suspended matter (Svensk standard 1983), pH (25oC) (Skoog et al. 1976, Svensk standard 1979) and conductivity (25oC)(Svensk standard SS 02 81 24 1985). Concentrations of DOC were measured using a Shimadzu TOC-5000 with test tube changer ASI-5000A (SS-EN 1484 - SIS) 2.2.2 Catchment analysis To describe the catchment area of each sample point (inlet) the software Quantum GIS (QGIS) was used together with integrated GRASS-modules. A raster of new national elevation data (nnh) from Swedish Surveying Authority was used. The module r.watershed was used to generate theoretical streams and associated sub-basins in raster format from an elevation raster data set. These generated rasters were “thinned” using the GRASS module r_thin and “vectorized” using GRASS module r.vectorize. The generated streams revealed which of the 5

small generated basins that connect and they were manually merged to greater basins representing the inlets for each sample point, i.e. the sub- catchments (fig.2). Areas of different land types and the areas of houses were calculated in Q-GIS by making intersections of the modelled polygons of basins and polygons of land types, achieved from the digital vector-format map of terrain (Terrängkartan), or of polygons of houses, achieved from the vector property map (Fastighetskartan). The average elevation of each catchment was generated by the Q-GIS module Zonal Statistics. Relationships between parameters were screened by principal component analysis (PCA) using PAST (PAleontological STatistics, University of Oslo) software and also a Pearson's correlation coefficient matrix was set up to show connections between all parameters. 2.2.3 Loads I calculated the transported amount per second, from all sub-catchments and from each of the analysed substances, i.e. the loads to Lake Viken, by multiplying the concentrations in streams with respective flow. Load = massin/time =Volumein /time* Conc.in 2.2.4 In-lake loss In-lake-losses per second of all measured substances were calculated. Loss (in lake)= (massin - massout )/time Loss per unit of time is expressed as the difference between total transport (m/t) into the lake and the total transport through the outlets (Brosundet and Göta kanal). 2.2.5Gradient in Lake Viken As the major outlet of Lake Viken is situated in the east end it could be assumed to be a flow of water from the west to the east. I looked at samples from different locations in the lake to see whether a gradient in concentrations exists. If it is so, the western part of the lake could be regarded as less affected by streams entering the eastern part.

2.3 Comparison of a natural bog and a drained bog At the same day as inlets to Lake Viken were sampled I also sampled water from the outlet of the drained bog and from another nearby natural bog, Myrhulta mosse (figure 2) and the same analyses were made as for the other sampling sites.

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3. Results 3.1 Historic compilation of Lake Viken

Susp.m (mg/l)

60 40 20

500 400

15

300

10

200

5

40

100 1970

1975

1980

1985

1990

1995

2000

2005

2010

NO2+NO3 NH4

0 2015 300 250 200

30

150 20

100

10

50

0

0 7.4

8

7.2

6

7 6.8

4 2 0 1965

Nitr (μg/l)

0 1965 50

Tot-N (μg/l)

600

20

6.6

pH PO4

pH

Tot-P(μg/l)

tot-N tot-P

Precip. (mm)

80

25

NH4 (μg/l)

600 500 400 300 200 100 0 700

100

0 30

MRP (μg/l)

TotP appears to vary quite coherent with precipitation but in the long run there is a decrease of phosphorus even though precipitation is increasing. Measurement of total nitrogen started 1987 and varies roughly in coherence with phosphorus, absorbance and precipitation. Phosphate decreases during the whole period and from 1990 there was an increase in pH (fig.3).

Abs A336(cm-¹)

Turb A336(cm-¹)

A historic picture is obtained by plotting the different parameters on a time line (fig.3). Turbidity and suspended matter, measured from year 1996, shows highest values in early seventies and quite high fluctuations between adjacent years until the mid eighties. From year 2005 there are greater fluctuations again and a high peak 2007. Precipitation and absorbance 12 3.5 vary in similar cycles 3 10 2.5 of about ten years and 8 2 6 shows an increase over 1.5 4 1 turbidity the investigated period. 2 0.5 susp.m. 0 0 The last years, 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010 2015 however, absorbance 160 900 precip 800 140 700 abs seems to level out. 120

6.4 6.2 1970

1975

1980

1985

1990

1995

2000

2005

2010

2015

Figure 3.Year mean values from outlet Forsviksån; turbidity(420nm), suspended material, absorbance (420nm), toN, totP, nitrate, nitrite, pH and phosphate. Annual precipitation in mm measured in Skara. The last data point are larger and represent the values measured in this study.

Patterns in the data of water chemistry available from year 1968 and onwards are visualized by PCA (fig.4). In the bi-plot earlier years group together with TotP, and more recent years group with absorbance, precipitation and pH. Thus, there is a trend of decreasing phosphorus concentrations and increasing precipitation, absorbance and pH over time. Turbidity accounts for a great part of variance but shows no obvious trend over time and no correlation with the other parameters. Precipitation and absorbance (DOC concentrations) are tightly linked to each other indicating absorbance and precipitation being positively correlated.

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Figure 4: PCA bi-plot. Years in rows and concentrations of parameters in columns. All values are standardized and a constant, c=3, was added to all to avoid negative values.

3.2 Snapshot of inflows and catchment analysis Concentrations, absorbance and turbidity of the water samples, and also the catchment composition were standardized and analysed by a PCA (fig.5). DOC and absorbance (A436nm) were closely related, and also related to proportion of mire in the sub-catchments. Turbidity and total phosphorus were related and both of them were quite related to suspended material which, in turn, seemed to be related to proportion of agriculture land in the catchment. A Pearson's correlation coefficient matrix was made for all parameters (Table 1). High correlation (R=0.97) for DOC and absorbance indicates that DOC is the main factor controlling colour and thus iron and manganese are considered of secondary importance and where not analysed for. Correlation between DOC-levels in streams and percentage of mire in the respective subcatchment areas of Lake Viken had an R-value of 0.65.

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Figure 5. PCA bi-plot of sample points (inlets) in rows and concentrations of parameters and proportion of land types in columns. All values are standardized and c=3 added. Variance explained by proportion of lake cover and forest cover where small and therefore excluded.

Table 1. Pearson correlation matrix of r-values between proportion of land-types in sub-catchments and measured parameters. Values higher than 0.5 or lower than -0.5 are bold. The p-value for r=0.5 is 0.025 and for r=0.4 p= 0.081 (sample size = 20). Correlations between land types and parameters are marked by a grey background. %farmland %forest %mire %lake altitude house/ha condukt pH 436nm filt turbidity susp. DOC Tot N NH4 Tot P MRP nitr. a a

%farmland%forest %mire %lake altitude house/ha condukt. PH 25 436nm filt.turbidity susp.[mg/l]DOC[mg/l]tot N [µg/l]N H4[µg/l] Tot P [µg/l]MRP [µg/l]nitr.[µg/l] 1.00 -0.66 -0.34 -0.30 -0.38 0.10 0.71 0.44 -0.05 0.43 0.56 0.08 0.39 0.23 0.59 0.46 0.33 1.00 0.21 -0.45 0.12 -0.10 -0.50 -0.57 0.38 -0.10 -0.10 0.32 0.09 0.24 -0.14 -0.02 -0.65 1.00 0.01 -0.39 -0.49 -0.36 -0.32 0.72 0.00 -0.17 0.65 0.35 0.19 0.10 0.22 -0.44 1.00 0.28 -0.14 -0.27 0.18 -0.39 -0.32 -0.39 -0.45 -0.47 -0.38 -0.42 -0.38 0.47 1.00 0.54 -0.15 0.07 -0.72 -0.58 -0.56 -0.78 -0.84 -0.57 -0.85 -0.82 0.26 1.00 0.23 -0.14 -0.60 -0.31 -0.18 -0.58 -0.50 -0.36 -0.34 -0.44 0.28 1.00 0.49 -0.24 0.41 0.50 -0.14 0.13 0.02 0.44 0.28 0.44 1.00 -0.43 0.25 0.28 -0.39 -0.09 -0.14 0.00 -0.13 0.42 1.00 0.40 0.27 0.97 0.83 0.54 0.52 0.64 -0.48 1.00 0.82 0.46 0.65 0.16 0.53 0.43 0.07 1.00 0.36 0.69 0.56 0.75 0.66 0.11 1.00 0.87 0.58 0.62 0.70 -0.51 1.00 0.70 0.81 0.84 -0.23 1.00 0.75 0.84 -0.29 1.00 0.96 -0.13 1.00 -0.16 1.00

nitr. is the sum of nitrate and nitrite.

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Also in this case the mean altitudes of each sub-catchment negatively correlated with DOC-levels (R=-0.78) Also TotP and TotN correlates negatively with altitude (R=-0.85, R=-0.84) Percentage of farm-land and phosphorus (R=0.59) and also farm-land and suspended matter correlated (R=0.56). 3.2.1 Gradient in Lake Viken Results from concentrations measured in Lake Viken (table 2)(fig.6) show gradients in turbidity and concentration of tot-P and DOC from the south west part of Viken (sample point:Viken 2, fig. 2) to the south east (Brosundet). No gradient was obvious for concentrations of DOC.

turbidity

0.012 0.010 0.008 0.006 0.004 TotP

12 10 8 6 4 2 0 0.16

12 10 8 6 4 2 0

0.15 0.14 0.13

420nm f DOC

G.kanal Tåtorp

Viken 1

Viken 2

Viken 3

Brosundet

Figure 6:Results for turbidity, TotP, absorbance and DOC from different locations in Lake Viken. See figure 1 for positions. From left:Viken1, Viken2, Viken3 and outlet Brosundet.

Table 2: Values measured In Lake Viken (23/11 2012). Sample points can be found in figure 2. [µg/l] [µg/l] (µg/l) [µg/l] mg/l Abs420/cm [mg/l] sample point turbidity DOC tot N NH4Nitrate+Nitrite susp m. TotP G.kanal Tåtorp 3.4 0.012 10 598 28 170 10 Viken 1 3.3 0.008 10 501 24 170 10 Viken 2 2.1 0.008 9 557 21 180 8 Viken 3 2.5 0.005 9 568 24 180 7 Viken mean 2.6 0.007 9 542 23 177 8 Brosundet 1.6 0.005 9 525 24 170 7

[µg/l] MRP 1 3 2 2 2 1

3.2.2 Loads To the western part of Lake Viken River Örlan (Örlenbron) and Åsen contributed most suspended material and tubidity. River Örlan contributed most DOC (8g/s) of which 25% (2g/s) originated from the drained bog Ryholms stormosse. For the whole of Lake Viken most of turbidity (7 abs*l/s) and suspended matter (4g/s) originated from the inlet Näs. Largest amounts of DOC came from River Edsån, which by far is the greatest inlet, and from the inlet Liaängen. River Edsån also contributed most tot-N and tot-P. (table 3). The concentration of ammonium (NH4) was high in the outlet from bog Ryholms stormosse. The contribution to the lake as a whole reached 15% even though the flow is very low.

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Table 3.Transports of substances (loads) from sub-catchments to lake Viken and in-lake losses.Top five sample points represent the inlets to the western part of lake Viken. The three rows below “Örlenbron” represent the transports just upstream the outlet from the drained bog Ryholms stormosse, the transport at the outlet from the bog and immediately downstream the outlet. sample point/outlet susp m [g/s] turb [abs*l/s] Örlenbron 2 5 Örlan upstream 1 3 Bog (Ryholm) outl. 0 1 Örlan downstream 1 4 Åsen 2 5 Fägre boda 0 0 Sjötorp-Gäddeb. 0 1 Hästabäcken 1 2 sum inflow western Viken 4 13

DOC [g/s] %of tot Tot N [mg/s] 8 569 6 367 2 4 112 8 663 2 203 0 4 1 42 1 83 13 900

Halnatorp Valön Vispås Liaängen Edsån Skarvudden Näs Sannum Rosendala Bjurbäcken Solviken Sum inflow to Viken

0 0 0 1 2 0 4 0 0 0 0 12

2 0 0 5 4 0 7 1 0 0 0 32

4 1 0 10 14 0 8 0 0 0 0 51

Brosundet(bron) G.kanal Tåtorp

8.0 1.3

25.0 4.2

45.9 3.8

a

28

NH4 [mg/s] %of tot Nitr. [mg/s]a TotP [mg/s] MPR [mg/s] 61 137 12 2 28 0 4 0 53 15 0 1 1 119 121 6 2 14 48 4 3 1 0 0 0 3 1 1 0 5 3 1 1 85 189 18 5

242 49 8 434 2220 16 878 35 24 4 1 4811

21 5 1 35 107 1 84 4 6 0 0 349

2676 226

120.8 10.8

31

flow [l/s] 806 598 42 759 90 2 24 35 957

15 1 0 45 1778 5 88 3 6 1 0 2132

2 1 0 3 9 0 7 0 0 0 0 41

1 0 0 1 -1 0 2 0 0 0 0 9

150 25 3 409 3420 14 549 32 22 6 1 5588

866.4 64.2

33.8 3.7

4.4 0.5

5096.4 377.8

sum of nitrate and nitrite

3.2.3 Loss Greatest in-lake losses (table 4) compared to the inflow transport was for NH4- N, nitrate-N +nitrite-N, MRP and tot-N. Only 3% of DOC was lost in the lake. There is a quite big difference in loss between suspended matter (23%) and turbidity (8%). Table 4. In-lake losses of parameters and in losses as percentage of total inflow of respective parameter. “Loss/inflow”represent the loss as proportion of the total transport of the parameter into the lake. sample point In-lake-loss (g/s) loss/inflow a

susp m [g/s] turb [abs*l/s] 2.8 2.5 23% 8%

DOC [g/s] Tot N [mg/s] 1.3 1909 3% 40%

NH4 [mg/s] Nitr. [mg/s] a 217 1201 62% 56%

TotP [mg/s] MPR [mg/s] 3.3 4.4 8% 47%

sum of nitrate and nitrite

3.3 Comparison of a natural bog and a drained bog Concentrations, absorbance and turbidity of the natural bog Myrhulta mosse and the drained bog Ryholms stormosse were compared (fig 7). Nitrate/nitrite showed no or little difference between sites. All other parameters were higher in Ryholms stormosse, especially suspended material, turbidity and phosphorus.

11

60

Ryholms stormosse Myrhulta mosse

7

50

6

40

5 4

30

3

20

2 10 1 0 conduct

DOC[mg/l]

tot-p [µg/l]

MRP [µg/l]

0 pH

turbidity

susp [mg/l]

tot N [mg/l]

NH4 [mg/l]

nitr/nitr[µg/l]

Figure 7: Comparison of results from analysed samples from the bog Myrhulta mosse (natural) and from the drained bog Ryholms Stormosse. (Nitr./nitr. is the sum of nitrate and nitrite.) Values for Ryholms stormosse were consistently higher than for Myrhulta.

4. Discussion 4.1 History The main changes in the water quality of Lake Viken from the late 1960s to the present are increased pH-values and absorbance together with decreasing concentrations of phosphorous. Absorbance and precipitation increased over the entire period. 4.1.1 DOC Absorbance at 420/436 nm and precipitation increased over the entire period, but fluctuated in synchronized cycles of about 10 years (fig3). Between 1965 and 1975 the high peak of absorbance reached 75 A436/cm. The last peak occurred around year 2000 and reached an absorbance of 130 A436'/cm. That is an increase of almost 75% in 30 years. The last cycle does not follow the same pattern as previously years. Where an increase would be expected from year 2005, based on previous years, absorbance is stabile, or even declining slightly. The most recent measurement however, which was the sample taken in this study, showed a higher value. Why this is so is unclear. The only large and recent operations in the catchment was the drainage of the bog Ryholms stormosse, which began 2011 and continued in 2012, and a nearby clear-cutting that was performed in 2010. Perhaps these actions contributed to changing water quality before the last sample. In samples taken from lake Viken in this study, absorbance and DOC concentration are highly correlated (R=0.97) and thus the absorbance can be used as a measure of DOC -levels that were not available in the historical data. The changes in DOC, precipitation and pH suggest that increased precipitation wash out larger amounts of humic substances, which also are more mobile due to higher pH in soils. Higher flows also means shorter retention time in the lake during which DOC can degrade by the action of UV-light (bleaching) and bacteria (Miller & Zepp 1995, Moran & Zepp 1997, Lindell et al. 1995). On the other hand, as already mentioned in the introduction, the relationship between DOC and precipitation may be more complex. Degradation of organic material to DOC in soils is dependent on both water saturation, temperature and also on the substrate i.e. the soil. Soils in the area are probably less water saturated today than a century ago as an effect of ditching. It is not clear how increased precipitation and perhaps higher temperatures will affect already drained soils. 12

The effect of pH also has more than one side. Increasing pH has been linked to increased wash out of humic substances from soils and also to a decrease in the ability of particles and DOC to form aggregates in the water column. DOC in aggregates may settle to the sediment due to the higher weight (Gerritsen and Bradley 1987, von Wachenfeldt & Tranvik 2008). Also UV-light is thought to facilitate the aggregation (von Wachenfeldt et al. 2008). 4.1.2 Turbidity Even though no change in turbidity could be seen it may be a change in what causes it. The historic data shows higher phosphorus concentrations in earlier years, which likely have promoted phytoplankton production (Schindler 1974), while higher DOC concentrations in more recent years are likely to have inhibited phytoplankton growth by light inhibition (Karlsson et al. 2009). Turbidity caused by phytoplankton thus can be assumed to have decreased as phosphorus decreased. Simultaneously, increasing terrestrial DOC may have induced production of particles by flocculation (von Wachenfeldt & Tranvik 2008) a process which may be promoted by UV-light (von Wachenfeldt et al. 2008). It is also feasibly that inflow of terrestrial particles has increased due to higher precipitation. To get a more detailed picture of the development of turbidity in lake Viken it would be relevant to investigate the sediment layers from present and back in time to test if there is a shift from phytoplankton residues to other kinds of particles of other origins. Other factors, as well, such as littoral vegetation, land use like drainage of the catchment and food web structure (i.e. fish species and zoo plankton) of the lake may be important factors to explain the level and nature of turbidity. According to people living close to Lake Viken, wide riparian zones were earlier covered by reed belts, but these disappeared during the 1980s. They testify about decreases in pike catches and increased amounts of Canadian geese since then. During the moulting period the geese forage in the water and by grazing on common reed therefore can reduce the prevalence of reed. In nearby Lake Vänern geese foraging on common reed have been shown to inhibit their propagation (Palm 2009). Less of submerged macrophytes may promote turbidity by increasing re-suspension of sediment and by increased erosion in the riparian zone by stabilizing the sediment and also functioning as breakwaters (Jackson & Starrett 1959, Dieter 1990, James & Barko 1990, Petticrew & Kalff 1992). Also phytoplankton are less abundant in macrophyte stands as a result of light and nutrient competition and also because they constitute refugia for zoo-plankton (Wium-Andersen et al. 1982, Timms & Moss 1984). A decrease in piscivores (e.g. pike) probably results in more bentivorous cyprinids that by foraging in the sediment also contribute to turbidity by causing re -suspension (Hansson et al. 1998). Increase in turbidity and colour (DOC) may result in a negative spiral of descending water quality. Piscivores will have difficulties finding their prey, i.e cyprinides, who by their foraging on bentic fauna, zoo -plankton and macrophytes continue to worsen the quality of water. Due to less sunlight penetration macrophytes will have difficulties to establish at the bottom. Absence of vegetation means destabilized sediments more prone to re-suspension. As mentioned above, suspension of sediment can induce the DOC production when it breaks down, and in this way loss of sediment stability also can contribute to higher DOC -levels.

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4.2 Snapshot -study 4.2.1 Gradient in Lake Viken In the western part of lakeViken the impact of river Edsån could be assumed less than in eastern part if there was a current from the west towards east. The gradient in DOC-levels from the western part to Brosundet in east was low, indicating quite good mixing of the water. This argues against the idea that Lake Viken should be considered as two parts where the eastern part has little influence on the western part. Suspended material, on the other hand, showed higher values in the western part and was declining towards the eastern outlet. 4.2.2 Loads The snapshot analysis of the inlets to Lake Viken showed large spatial differences in concentrations and transport. River Edsån, which is the major inlet, had much lower concentration of DOC than the lake it self but contributed most DOC due to high flow. 4.2.3 In-lake loss The lack of a gradient in DOC along the lake concomitant with a decrease in particles supports that the loss of particulate material by sedimentation is faster than the degradation of DOC. Hence, sedimentation occurs at a time scale faster than the mixing of the lake, while DOC is lost at a rate that is slow compared to the mixing of the water throughout the lake basins. Loss of turbidity and suspended matter was 8% and 23% of ingoing amounts. Turbidity is the difference between absorbance of filtrated water and unfiltered. A reason for less loss of turbidity than of suspended material could be that heavier particles (mineral) were replaced by lighter (plankton). This change in kind of particles affects mass of suspended material but maintain turbidity. 4.2.4 Correlations Proportions of mire in sub-catchments correlate positively with concentrations of DOC. This results where expected as wetlands are important sources of DOC (Eckhardt & Moore 1990). Wetlands has also been shown to have particularly high contribution to water DOC-levels during low flows (Laudon et al. 2011), which was the case when the samples where collected. At higher flows, forest covered land could be expected to be of higher significance for DOC. Altitude correlated negatively with levels of DOC and nutrients (tab.1). This is consistent with earlier studies (Hope et al. 1997). The pretty weak correlation between proportion of mire in sub-catchments and altitude (R = -0.38), suggests that not merely the absence of mire makes upland areas emit less DOC. Mire and low-land seems to be most important terrain-factors for DOC -levels run -off water. At higher precipitation and flows forested areas may increase in contribution. Agricultural land correlates positively with conductivity, turbidity, suspended material and phosphorus.

4.3 Importance of the drained bog Ryholms stormosse The contribution of DOC from the bog Ryhoms stormosse was about 15% to the western part of lake Viken and 4% to the whole lake. Further investigations are necessary to define the impact of the drainage. Compared to the intact bog, Myrhulta mosse, the DOC-level was about 50% higher in the bog Ryholms Stormosse. The results are supported by previous 14

studies in which drainages of blanket bogs and peat covered catchments have been shown to increase the release of DOC (Conway & Millar 1960, Mitchell and Mc Donald 1992, Holden et al. 2004).Based on the measured transport and the difference in concentrations in water from the two bogs, the drainage may have increased the contribution of Ryholms Stormosse to Lake Viken as a whole by about 2 % units. Drainage of other land areas and factors as higher precipitation, pH and forestry are likely to have contributed to higher DOC -levels as well. According to the Water Owners Association of Lake Viken and also the peat mining company, Rölunda produkter, there has been a major emission of sediment in 2010 upon ditching. This is said to have affected the lake much at the time. Future emissions of sediment may be avoided by improved sedimentation ponds. However, a Canadian study indicated that the ponds have to be very large and the cleaning process must be carefully conducted not to generate loss of sediment (Pavey et al. 2007). Suspended sediments concentrations (SSC) in run off from drained and harvested bogs in Canada has been shown to be significantly higher than from natural bogs (Pavey et al. 2007). The recommended daily maximum concentration issued in the current Canadian province was 25 mg suspended sediment. This limit was exceeded 30% of the time for natural bogs and 70% of the time for harvested bogs. More extreme loads of 500 mg/l or more was present only 4% of the time in a natural bog but 30 % in harvested bogs (Pavey et al. 2007). The loads are highest in autumn and spring when flows are highest. The ratio of drainage area to pond volume (m2/m3) could in part explain the difference between different harvested mires. A higher m2/m3 -ratio was shown to be related to higher SSC. The mean ratio in the study was 240 m2/m3. Transferred to Ryholms stormosse this ratio suggests a total pond volume of 23000 m3 if a harvested area of 550 ha is assumed. Considering ponds to be 5 m wide and 2 m deep, the total length of ponds should be 2.3 km to give a total volume of 23000 m3. But the study showed that the volume of the settling ponds was not sufficient. Entertainment of dams could have both good and bad effect on retention efficiency. The cleaning process may release material to the streams. Comparison with the Canadian study above shows that the measured values for suspended material in this study are low, 1mg/l for natural the bog Myrhulta mosse and 3 mg/l for the drained bog Ryholms stormosse, and that much higher values could be expected by higher flows. This further support the assumption that emissions of suspended material occur very intermittently and that attempts for measurements has to be continuously conducted in order to monitor the transported amounts. The ammonium (NH3 – NH4+) concentration in the drainage water from the bog Ryholms stormosse was remarkably high. Ammonium can affect lake-ecosystems in several ways depending on current physical conditions. Acute poisoning of fishes and other aquatic animals is caused by non ionic ammonia. Particularly sensitive species have given us limits that should not be exceeded. Harris et al. (1998) proposed that concentrations of ammonia (NH3) should never exceed 0,01-0,02 mg/liter. This was not exceeded in river Örlan nor in the main drainage stream of the bog Ryholms stormosse where the measured NH4-concentration was 1.28 mg/litre. According to (Emmerson et al.) the proportion of NH3 could be assumed be 0,0397 % of NH4 at pH 6.0 (pH 5.9 was mesured at the main drainage stream.) and a temperature of 20 Co. This would result in a NH3-concentration of 0,0003 mg/l and wich would be harmless.

15

4.4 Conclusions and outlook The most obvious changes in water quality in lake Viken, from year 1965- 2012 were increased pH and DOC-level and decreased concentration of tot-P. Precipitation increased in the same pattern as DOC. Turbidity showed no trend but perhaps it has been a change in origin of particles. High proportion of mire and low altitudes seem to be the most important landscape-factors to explain high DOC-levels. The drainage of the bog Ryholms stormosse increased the transport of DOC to lake Viken about 2%. Measurements of transport of suspended matter have to be conducted continuously during a long period. This was not the case in this study. Anyway, the concentration of suspended material was much higher in water from the drained bog. In order to slow down further browning of lake Viken, blocking of ditches in peat-soils and less forestry activity, could be done on the shorter term. On longer term it may be important to reverse the trend of global warming. The turbidity of the lake could possibly be decreased by increased reed-belts as a result of geese-hunting. It is also important to improve conditions for piscivores.

5. Acknowledgments Thanks to Anders Ahlenius and Herbert Andersson in Töreboda for hosting and guiding around lake Viken, Jan-Erik Johansson for help in lab, Lisa Olausson for walking with me around the bog Ryholms stormosse, Lars Tranvik for supervising, Jovana Kokic for opposing and Anna-Kristina Brunberg for refining this report!

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Appendix 1: Historic data on water chemistry from channel of Forsvik and precipitation in Skara. 1976 1977 1978 1979 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012

481 826.8 552.4 645.1 641.7 611.7 422.9 517.9 476.5 724.8 523 594.9 656.1 503 612.3 595.4 521.9 602.6 579.1 703.2 551.5 566.6 778.3 675.9 709.3 677.7 646.1 647.3 741.8 614.6 672.1 803.4 793.9 664.7 781.5 854.3

16.08 18.25 19.42 25.42 21.33 17.83 17.17 16.67 14.75 14.67 13.17 14.58 12.75 18.33 18.33 20.00 18.33 14.67 16.00 13.67 11.58 22.00 17.08 13.08 12.17 12.50 13.67 11.58 9.30 11.00 8.33 12.00 16.25 10.00 11.18 10.85 7

7.17 8.82 9.35 8.53 8.13 7.98 7.84 7.25 8.10 7.71 7.14 9.28 9.09 8.46 7.94 8.11 9

26.92 51.42 66.33 66.08 69.58 79.67 73.50 60.83 53.92 66.42 79.42 76.42 94.42 80.67 72.50 75.08 68.58 61.50 76.17 84.92 69.92 71.67 101.36 124.33 96.42 116.50 102.67 78.25 79.75 71.92 71.08 104.75 105.25 97.92 95.25 97.75 148.7

6.80 6.70 6.69 6.71 6.70 6.74 6.76 6.85 6.79 6.79 6.73 6.77 6.69 6.67 6.62 6.74 6.74 6.76 6.77 6.85 6.84 6.79 6.86 6.82 6.89 6.85 6.91 6.91 7.13 7.18 7.02 7.13 7.26 7.24 7.03 6.93 6.96

6.00 4.17 3.75 3.75 4.25 4.42 3.17 2.42 3.58 2.50 2.50 4.75 2.33 4.17 3.25 2.33 3.75 3.17 4.33 3.67 4.08 2.67 2.42 1.92 2.00 2.17 3.17 2.00 1.79 0.79 3.08 2.75 1.13 2.00 0.71 0.63 1

23.08 34.00 28.75 19.33 20.00 16.50 11.92 10.08 14.50 14.50 10.08 12.92 10.58 14.33 15.75 16.00 13.00 11.92 11.92 20.50 13.25 9.83 10.64 11.92 15.17 20.00 17.33 19.83 35.67 45.00 26.33 38.75 23.00 35.00 10.42 9.79 24

81.50 204.42 227.25 204.92 166.75 172.50 191.33 122.83 139.17 180.92 212.92 237.75 258.33 159.75 135.75 128.67 115.67 87.50 109.42 118.17 110.33 96.25 147.67 216.00 176.25 211.67 141.33 98.42 120.67 94.33 116.83 176.83 116.33 111.08 123.04 106.04 170

504.29 599.17 520.00 459.92 526.25 476.08 446.00 468.00 516.25 470.83 586.33 579.00 656.67 547.23 532.00 547.67 500.75 424.67 400.00 430.00 486.67 418.33 375.00 460.00 443.33 525

4.35 6.07 7.92 5.05 7.38 8.13 5.90 6.28 4.87 4.95 5.05 5.38 5.95 8.38 8.10 7.80 8.27 6.90 6.03 6.60 6.50 6.28 8.38 6.55 7.07 6.93 6.53 6.65 5.42 2.45 7.00 9.62 3.31 6.55 6.40 7.52 4.9000

2.63 2.38 2.97 2.21 2.30 2.49 2.58 2.01 1.91 1.43 1.48 2.35 1.85 1.03 1.40 1.57 1.6

35 47 28 25 26 26 30 29 38 41 27 34 50 45 43 40 43 46 36 52 41 26 38 41 41 79

Appendix 2. Results from sampling of rivers and from lake Viken and bog Myrhulta mosse. [mS/m] plats kondukt 25°C Fägre boda 87.7 Åsen 137.6 Halnatorp 47.9 Valön 54.6 Vispås 51.4 Liaängen 49.5 Sätraån 51.7 Skarvudden 99 Näs 69.8 Sannum 56.8 Rosendala 79.2 Bjurbäcken 66.8 Örlenbron 106.6 Mossen spetsb. 49.3 Örlan upp 111.8 Örlan ned 106 Hästabäcken 78.6 G.kanal Tåtorp 67.8 Brosundet 64.5 Solviken 94.2 Sjötorp-Gäddeb. 83.8 Myrhulta mosse 36.4 inf.Stormossen 62 Viken 1 Viken 2 Viken 3 Viken medel

65 63.5 66.6 65.0

pH 25°C 5.78 6.95 5.85 4.31 4.83 6.25 6.38 7.06 6.77 6.37 6.55 3.38 7 5.87 7.09 6.99 6.31 9.92 6.96 6.54 6.19 5.17 3.88

5cm 436nm filt 0.617 0.510 0.529 0.969 0.971 0.440 0.042 0.134 0.259 0.297 0.123 0.159 0.107 0.934 0.081 0.145 0.682 0.120 0.115 0.176 0.493 0.538 0.899

5cm 420nm filt 0.783 0.645 0.668 1.204 1.207 0.558 0.054 0.176 0.329 0.375 0.159 0.207 0.137 1.151 0.105 0.185 0.863 0.154 0.149 0.232 0.628 0.667 1.136

5cm abs436of 0.683 0.783 0.588 1.021 1.053 0.497 0.048 0.148 0.327 0.389 0.198 0.165 0.137 1.070 0.108 0.172 0.996 0.176 0.140 0.233 0.616 0.574 0.958

7.07 7.03 7.14 7.1

0.112 0.107 0.107 0.109

0.143 0.138 0.138 0.140

0.150 0.145 0.131 0.142

5cm Abs436/cm Abs420/cm mg/l abs420of turbiditet turbiditet susp m Medel 0.856 0.013 0.015 14.7 0.945 0.055 0.060 18.0 0.734 0.012 0.013 3.3 1.262 0.010 0.011 2.3 1.303 0.016 0.019 4.0 0.623 0.011 0.013 2.8 0.061 0.001 0.001 0.4 0.192 0.003 0.003 1.3 0.404 0.014 0.015 7.9 0.478 0.018 0.021 4.6 0.249 0.015 0.018 12.6 0.214 0.001 0.001 1.2 0.171 0.006 0.007 2.1 1.302 0.027 0.030 3.3 0.136 0.005 0.006 1.7 0.214 0.005 0.006 1.3 1.228 0.063 0.073 17.2 0.212 0.011 0.012 3.4 0.174 0.005 0.005 1.6 0.283 0.011 0.010 3.1 0.769 0.025 0.028 7.9 0.712 0.007 0.009 1.2 1.200 0.012 0.013 1.0 0.183 0.178 0.165 0.175

0.008 0.008 0.005 0.007

20

0.008 0.008 0.005 0.007

3.3 2.1 2.5 2.6

[mg/l] DOC 38 27 28 46 46 24 4 14 15 15 11 13 10 46 10 11 42 10 9 17 30 28 50

[µg/l] tot N 2437 2258 1616 1945 2261 1060 649 1124 1600 1103 1092 679 706 2680 614 873 2375 598 525 879 1732 1357 1195

[µg/l] NH4 506 157 137 196 288 87 31 54 153 112 263 42 76 1277 48 156 156 28 24 63 134 650 86

[µg/l tot P] 64 45 16 20 26 8 3 13 13 10 16 11 14 19.4 7.1 8.2 34 10 7 8 40 7 6

10 9 9 9.3

501 557 568 542

24 21 24 22.7

10 8 7 8.2

[µg/l (µg/l) MRP Nitrat+Nitrit 49 76 28 530 7 100 17 31 22 90 3 110 0 520 3 380 4 160 4 82 7 280 2 150 2 170 18.4 <1 0.7 180 2.1 160 17 98 1 170 1 170 2 130 21 36 6 <1 14 <1 3.3 1.7 1.6 2.2

170 180 180 176.7