1

Abstract Monitoring and managing water quality has become an increasingly important issue in response to the EU Water Framework Directive. It is widely recognised that anthropogenic nutrient inputs can cause adverse environmental effects within a fluvial system, and therefore establishing the major sources of these inputs is vital if the UK is to meet the WFDs good ecological standard guidelines. This study focused on determining the relationship between land use, management location, seasonality and chemical water quality within two rivers in the Trent catchment; the Dove and the Tame. Triplicate water samples were obtained at 20x400m intervals during two points in the year along an 8km section of each river. Spectrophotometry analysis provided concentrations of NO3- (NO2-)-N, NH4+-N and PO43- -P, while pH and dissolved oxygen concentrations were obtained on-site. Surrounding land use zones (urban, arable, livestock and wetland) and management location were established using satellite imagery. The water quality parameter data was divided into sub-groups depending on the month of data collection and location of the site in relation to management and land use. Arable land was the biggest contributor towards NO3- (NO2-)-N and PO43- -P pollution, increasing mean concentrations by 16% and 9% respectively compared to urban sites and 79% and 96% compared to livestock sites. NH4+-N concentrations remained similar throughout arable, urban and livestock land uses but decreased by up to 85% at wetland sites. Paired sample t-tests confirmed that seasonal variations in parameter concentrations were significant in all land use zones, however pH and DO variation were later attributed to natural drivers. It was further shown that chemical water quality parameters were not significantly lower at managed sites on either river. The findings of this study could be used to evolve prevention and mitigation management strategies in the Trent basin.

Table of Contents

Abstract ..................................................................................................................... 2

List of Figures, Tables and Appendices .................................................................... 4

1. Introduction ..................................................................................................... 5-10

2. Methodology ................................................................................................. 11-13

3. Results ........................................................................................................... 14-29

3.1 Seasonal variation ....................................................................... 14-17 3.2. Spatial variation.......................................................................... 16-21 3.3. Inter-river variation .......................................................................... 21 3.4. Land use and management on the Tame .................................... 21-24 3.5. Land use on the Dove ................................................................. 24-27 3.6. Management on the Dove........................................................... 27-29

4, Discussion ..................................................................................................... 30-37

4.1. Acceptable chemical health ........................................................ 30-31 4.2. Controls on water quality ........................................................... 31-36 4.3. Management recommendations.................................................. 36-37 4.4. Limitations ....................................................................................... 37

5. Conclusion..................................................................................................... 37-38

6. References ..................................................................................................... 38-42

7. Appendices .................................................................................................... 43-45

List of Figures, Tables and Appendices Figures Chemical health parameter concentrations on the River Dove in November and March ............................................................................................. Figure 3.1 Chemical health parameter concentration on the River Tame n November and March .............................................................................................. Figure 3.2 The Simple Moving Average of parameter concentrations along each river course in November and March ................................................................ Figure 3.3 Parameter concentrations before and after management (and land use change) on the River Tame in November and March .................................. Figure 3.4 Parameter concentrations before and after land use change on the River Dove in November and March ............................................................... Figure 3.5 Parameter concentration distribution characteristics (box plots) of sample sites at weir-managed and non-managed locations on the River Dove in November and March ............................................................... Figure 3.6. Calculation chart used for inferring DO saturation percentage from DO mg/L data during the discussion ................................................................. Figure 4.1 Tables DO saturation percentage of DO 3-7mg/L in both rivers at varying seasonal water temperatures ......................................................................... Table 4.1 Appendices Correlation coefficient values for NO3- (NO2-) - N, NH4+-N and PO43- -P standards during each run of the AA3 .................................................. Appendix 7.1 A comprehensive list of all data points excluded from the results section ............................................................................................................. Appendix 7.2 The distribution characteristics of each data set; including excess kurtosis and Sharipo-Wilks values .................................................................. Appendix 7.3 An overview of some of types of statistical tests used in the Study ........................................................................................................................... Appendix 7.4 Estimated percent total ammonia present in the toxic, un-ionized ammonia form in a zero salinity solution ............................................... Appendix 7.5 4

Introduction

1.1 The importance of good water quality in a riverine system

Historically rivers and estuaries were used as a source of food, however more recently they have been exploited for multiple purposes, ranging from transport and communication to industry and development (Tinsley, 1998). While traditionally these exploitations have had negative implications on water quality many modern uses of rivers actively require certain levels of quality and thus the complex relationship between humans and the chemical health of a river is a paradoxical one. Good water quality promotes a multitude of economic, social and ecological benefits and is paramount to sustainable development (Defra, 2010), recreation (Douglas et al., 1986), farming (Hooda et al., 2000; Tilman et al., 2002) and general environmental responsibility in the future.

From a monetary perspective a clean river system and the resultant array of ecosystem services can stimulate the growth of regional and national economies (Bagstad, 2006). Estimations regarding the total worth of UK rivers are ongoing and the Natural Capital Committee are leading a study which aims to provide the government with a better understanding regarding the value of healthy wetland areas (Defra, 2012). This direct value can be simply understood within regions of outstanding natural beauty, which are areas often associated with pristine fluvial environments. Here the cultural services provided to human populations can generate vast quantities of money via entry fees and charity donations (National Trust, 2012). Clean rivers can also help mitigate the costs of the provisioning services we obtain from them, for example waters high in nutrients and organic matter are expensive to render useable from a drinking perspective (Vickers, 2001). Clean source water limits the use of ozone gas injection and granular carbon activated treatments within the drinking water industry and helps to reduce economic and environment costs (Severn Trent, 2012). Particularly high or low pH levels, which are regularly associated with low quality waters (NASA, 2012), also cost the UK large amounts of money in pipe work and other infrastructure repairs (Severn Trent, 2012). Carson and Mitchell (2010) quantify these benefits in their study, asserting that the economic advantages of reducing pollution in rivers far outweighs the costs of doing so.

Further to the economic benefits of good quality river water it is widely acknowledged that the aesthetic properties of a healthy looking river provide a multitude of social benefits. Recreation activities like fishing are facilitated by clean rivers (Salazar et al., 2009) while a recent study by Bosco (2005) has helped determine the linear relationship between a healthy aquatic ecosystem and social wellbeing. The limitation of potential health threats due to clean water can also have far reaching social benefits and improve both the quality of life and standard of living of communities whom are less affected by these threats (kjellstrom et al., 2007).

From an ecological perspective clean river waters are important for protecting and encouraging high levels of biodiversity. Levels of marcophytes, macroinvertebrates and general species richness within river systems are shown to decrease as pollution increases (Azrina et al., 2005). Mainstone and Parr (2002) assert in their study that this decrease in biodiversity is primarily caused by alterations in the competitive balance between species via the introduction of foreign elements. The Water Framework Directive [WFD] has recently recognised the importance of an individual rivers ecological status and has instructed that all EU member states water bodies must meet good ecological standards by 2015 (WFD, 2007). It is becoming increasingly important to find the major drivers of poor water quality in order to fairly delegate the costs of meeting these standards (Bateman et al., 2006).

1.2. The drivers of water quality in riverine system

Both natural and anthropogenic factors can drive the quality of water within a river and it is accepted that many factors often work in tandem to dictate overall quality. Quality can be assessed in a variety of ways but is predominantly viewed by the Environmental Agency [EA] and other organizations from a biological and chemical perspective (EA, 2013). Nutrient levels, pH, biological oxygen demand and biodiversity status are the common tools used globally when attributing a magnitude of water quality to a river, however it is widely understood the former three chemical parameters are good indicators and drivers of biodiversity (Vorosmarty et al., 2010; CBD, 2010).

Nutrients, pH and oxygen levels within the river system can be influenced by natural forces including the surrounding geology, biological activity and climate variations. Concentrations of dissolved oxygen [DO} within the water can be a product of natural levels of aquatic flora, while flow dynamics and temperature have also been shown to have major influences on DO via aeration and solubility changes in terrestrial water bodies (Papagiorigio, 2012). The pH of river water is naturally dictated by the mineral composition of the surrounding soils and rocks however certain atmospheric compounds may induce acid rain and cause short-term changes. In pristine catchments geological and biological processes are the dominant source of nutrients while short term climatic changes, e.g. acid rain (Wood and Bormann, 1977), have been continually shown to cause temporal fluctuations in their abundance (McKee et al., 2001).

Pristine fluvial environments are becoming increasingly uncommon due to the rise of intensive agriculture, urbanisation and atmospheric pollution. Only 6% of rivers in the UK have been classified as of high ecological standard by the WFD report of 2012 and the more than 60% fall below the guidelines standards of good (WFD, 2012). Anthropogenic sources of nutrient within rivers are predominantly derived from the agricultural sector, inorganic nitrogen in the form of nitrate and ammonium nitrate and phosphorus compounds in the form of phosphoric acid are used in almost every inorganic fertiliser worldwide and excessive use or unfavourable weather conditions have been shown
6

to cause leaching and run-off problems (Haygard and Jarvis, 1997). The problem is usually worse on arable land, however feed crops within a livestock farm can also require large amounts of artificial fertilizer depending on soil type and previous levels of agricultural intensity (Kersebauma et al., 2003). Livestock farming itself can cause point and diffuse pollution of the river through slurry, manure, and silage leakage as well as direct animal wastes (Hooda et al., 2000). Moreover Mallin (2000) states that during unfavourable weather events industrial animal production can degrade water quality at higher rates than any other form of farming. In urban areas car exhausts produce oxides of nitrogen which can enter waterways in inorganic form during precipitation events (NPI, 2009), while detergents, lawn fertilizers and industrial wastes can result in point sourced entry of nitrates and phosphates to the river system through sewage networks (Butler and Davies, 2004). pH and DO can be affected by human activities as high levels of artificially derived algal growth increase levels of photosynthetic bi-carbonate ion production, cellular respiration and bacteria decomposition (Selman and Greenhalgh, 2009).

1.3 How can we improve and ensure good water quality?

In order for specific policy requirement regarding the state of rivers to be met it is important that effective prevention and mitigation pathways are understood and established. Prevention practices can occur in a multitude of formats ranging from limiting fertiliser use (Mapp and Barnado, 1994) to increasing sewage treatment of urban waste (Karr et al., 1995). Mitigation in the format of management is widely used around the globe with many schemes focusing on specific water quality increases while some flood and recreation management have water quality co-benefits. The logistics of water quality management are often difficult and a study performed by Pollard et al. (2001) outlines the social, political and economical problems facing management teams. Managing water quality requires the causes to be fully understood and therefore establishing the major drivers is vital.

1.4 Study Sites

This study focuses on a small section of two rivers within the Trent catchment area; the River Dove and the River Tame.

1.4.1 The River Dove

The Dove is located within the Peak District National Park, Derbyshire. Its waters rise out the limestone ground of the Axe Edge hill and flow southwards for 72kms until its confluence with the River Trent (PDNPA, 2012). The 7.6km section of the river viewed in the study can be seen in Figure 1.3. This section of the river has remained relatively unmanaged throughout history; recently however rock weirs have been implemented to promote favourable fishing conditions (Leaniz, 2008). Over
7

90% of the land use in the area is devoted to livestock farming and very little of the region has been urbanised (PDNPA, 2012). A summary of the current land use and management can be viewed in Figures 1.1 and 1.2a.

1.4.2 The River Tame

The Tame is located in the West Midlands. It rises near Oldbury and flows north-east for 40kms until its confluence with the River Trent. The 8km section of the river viewed in the study can be seen in Figure 1.3. This section, along with most other parts of the river, is heavily managed, both for flood risk and water quality purposes. The river was classified by the Trent River Board [TRB] as a threat to public health in the 1950s. That classification, along with the growing demand for safe drinking water, led to the implementation of the Lea Marston Purification Lakes in 1982. These lakes [Figure 1.2b] are designed to slow water velocities which allow pollutants to flocculate and settle in the sediment; this sediment is then dredged and discarded of (Rofe, 1994). The river section flows through both arable and urban land and a summary of this land use can be viewed in Figure 1.1.

River Tame

River Dove

Direction of flow

Direction of flow

Figure 1.1: Land use maps displaying the major uses of the land immediately surrounding the Dove and Tame sections of river. The maps were compiled using satellite imagery from the Google satellite GeoEye 1 (2013a) (2013b)

1.5 Previous studies and existing data

1.5.1 Literature

There have been no notable peer reviewed studies regarding the chemical water quality of the River Dove. The River Tame on the other hand, due to its polluted history, has received more academic attention. The majority of the studies, such as work by Aston and Brown (1975) and Beevan et al. (2000) focus on the ecological impacts of high pollution levels. Other studies focus on concentrations of particular indicators to infer pollution levels (Harkness, 1982; Austin, 2003). Few studies attempt to explain or establish the drivers of the documented pollution on the Tame.

1.5.2 Environmental Agency data

In recent years the Environmental Agency (EA, 2012) has been testing for Phosphate and Nitrate Concentrations along 5km stretches of both rivers. Their findings would suggest concentrations on the Tame display large spatial variation. Conversely concentrations on the Dove appear to vary very little along the river course. Determining the causes of this spatial variation will be important if future management and mitigation is to be successful.

1.6 Study aim and objectives

The study aims to assess the impact of current land use upon the chemical health of two rivers in the Trent catchment during different time periods and to determine if current management is mitigating these impacts. The studies objectives are shown below;

- To determine whether the rivers meet the standards proposed by various environmental bodies and organisations by collecting and analysing concentrations of certain chemical health parameters. - To determine whether these parameters vary spatially along the river course and to assess whether any variation is a response to land use and management practices. - To clarify the extent of seasonal variations in the parameters. - To use previous studies and literature to determine the extent factors external to land use and management are having upon the parameter concentrations and seasonal variations. - To combine the information gathered from this and other studies to suggest a management policy for the future.

Figure 1.2 [a]: Location of Recreational small weir management on the River Dove. Locations were obtained from Ordinance Survey maps and were plotted against the river course using GeoEye-1 (2013) satellite imagery.

Figure 1.2 [b]: Location of water quality management on the Tame. The location of purification lakes one and two were obtained from Ordinance Survey maps and plotted against the river course using GoeEye-1 (2013)

Site A

Dove

Direction of flow

Site T

Site T

Tame

Direction of flow

Site A

Figure 1.3: These maps show the location of the River Dove and River Tame sections in relation to the wider Trent catchment (GeoEye-1, 2013c). The red dots display the location of each sample site [A to T] along each water course. These 20 sample sites were evenly spaced at 400 metre intervals along each river section with the exception of two sites [E and F] on the River Tame which were spaced at an 800 metre interval due to accessibility problems. Site locations were designated before sampling using Ordinance Survey maps and the meandering nature of both rivers was accounted for during site designation. 10

2. Methodology

The study was primarily based around the collection and analysis of quantitative data and it mirrored techniques and methods used in previous studies. It focused on five chemical indicators which have been shown in literature to signify a rivers health status (Rothwell et al., 2009; ElbazPoulichet et al., 1999; Caraco et al., 2000). All data collected by the study was sourced over two sample events during November 2012 and March 2013, with laboratory work performed 3-5 days after each sampling period.

2.1 Chemical Health Indicators

The Chemical indicators chosen were nitrate/nitrate [NO3- (NO2-)-N] [mg/L], ammonium [NH4+N], [mg/L], orthophosphate [PO43- -P] [mg/L], pH and dissolved oxygen [DO]. 2.2 Data collection

pH and DO testing was performed on site while water samples were obtained and stored in order to perform nutrient analysis in the laboratory at a later date. The sampling was performed at 20 sample points along each river stretch [figure 1.1] at 400 metre intervals; at each site triplicate truereplicates were collected. Samples were always taken at 10 cm depths at the point of fastest flow for consistency and to avoid surface contaminants (Higgings, Grennan and McCarthy, 2007). All equipment used during collection [plastic sample pole, filters and syringes] were rinsed with DI water after each use.

Immediately after collection the water samples were tested for pH using a Eutech Cyberscan field pH meter. Environmental Protection Agency precautionary practice and calibration procedure was adhered to during each sampling period (EPA, 2012); i.e. calibration was performed after each sample day using pH buffer solutions and the probe was rinsed with DI water after each use. A subsample of each triplicate water sample was transferred to a 2ml test tube containing two dissolved oxygen tablets. Procedure outlined by the University of New South Wales (2012) was followed and DO concentrations to the nearest mg/L were recorded via visual interpretation of the sample colour.

The remaining water sample was immediately syringed through a GF/F glass microfiber filter to remove particles above 0.7 m. Filtration helps to avoid storage artefacts due to the cycling of NO3 - (NO2-)-N, NH4+-N and PO43- -P and reduced problems associated with light scattering during spectrophotometry analysis (Plymouth University, 2012).

11

The average water temperature of each river was obtained during both months from the Centre for Ecology and Hydrology (2012). This data was used later in the study to infer NH3 and DO % saturation from the recorded values of NH4+-N and DO [appendix 7.5; Table 4.1]. 2.3 Storage

The filtered water samples for nutrient analysis were stored in sealed 15ml plastic tubes and kept in the dark at ~4C in a cool box while on site during sampling days. After all 20 sites had been completed samples were kept at -21C in a freezer until laboratory use in order to preserve nutrient concentrations (Tang et al., 2001). Thawing of samples was performed one hour before analysis by submerging the tubes in tepid water. Nutrient removal and losses shown in studies by Watts et al. (2010) and Kotlash (1998) outline the drawbacks of filtration. It was deemed that these losses were unavoidable and would not impact upon comparison aspects of the study because the procedure and resultant nutrient losses were consistent throughout sampling.

2.4 Nutrient Analysis NO3- (NO2-)-N, NH4+-N and PO43- -P concentrations were measured in the laboratory with a Bran & Luebbe AutoAnalyser 3 [AA] within 3-5 days of sample collection (Naddeo et al., 2011). A stock solution of 1000mg/L KNO3 (NO3) N, 1000mg/L (NH4+) SO4 (NH4 N), 1000mg/L KH2 PO4 (PO4 P) was used to create standard dilutions for AA calibration. A new set of standards were prepared for each week of testing. The AA was calibrated to measure concentrations of NO3- (NO2-)N, NH4+-N and PO43- -P to 2mg/L with detection limits of 0.003 mg/L for NO3- (NO2-)-N, 0.01 mg/L for NH4+-N and 3 g/L for PO43- -P (Ryen, 2006). The AA calibration standards were of good quality and the correlation coefficient values for NO3- (NO2-)-N, NH4+-N [y=bx+a] and PO43-P [y=cx22 + bx +a] were well above the 0.97 minimum acceptable value (Ryen, 2006) as well as being consistent throughout testing [appendix 7.1]. 2mg/L drift samples were run for every 10 nutrient samples, drift was minimal throughout testing [+0.018; - 0.042 mg/L]. During AA testing it became apparent concentrations of NO3- (NO2-)-N for the majority of the River Dove samples and all River Tame samples would exceed the maximum measurement levels so 10-fold dilutions of NO3- (NO2-)-N samples and deionised water were created and run again using the same standards. During both rounds of testing [November and March] the AA displayed PO43- -P concentrations on the River Dove consistently close to the machines detection limits, sometimes displaying negative concentration values. PO43- -P concentrations on the Dove and Tame were adjusted in accordance with the AA baseline drift level during each run (-0.025mg/L, -0.019mg/L, -0.024mg/L and 0.011mg/L).

12

2.5 Quality control and data exclusion

At each site triplicate true replicates were taken and sampled. From the triplicate values Percentage Relative Standard Deviation [%RSD] was calculated and any NO3- (NO2-)-N, NH4+-N, pH or DO samples with a %RSD value of above 30 were excluded from the study [appendix 7.2]. This %RSD threshold, which is fairly high, is a product of using true-replicates as opposed to pseudo-replicates. This form of replication often increases variability in scientific study (Prosser, 2010) and therefore the higher %RSD threshold was set. This higher threshold allows for the inclusion of enough data to perform statistical analysis. %RSD variation between diluted and non-diluted samples was minimal (+2.2%; -3.1%). No %RSD threshold was set for the PO43- -P data because the low values on the Dove were close to the AAs detection limit and therefore variation between replicates was high. The data has been included in the study for between river comparison purposes however the results are used with caution. All PO43- -P Tame data was below the threshold. Throughout data analysis the raw data for each chemical health indicator was broke down into subgroups in accordance with the studies objectives; outliers were removed at each stage of analysis using the statistical software package SPSS [appendix 7.2].

2.6 Statistical method

The Sharipo-Wilks test was run on all data sets in order to determine whether to perform parametric or non-parametric tests. 17 of the data sets displayed p values of >0.05 and were therefore deemed to be normally distributed. As a further precautionary measure Q-Q plots were visually interpreted; all 17 sets followed similar trends to that of the theorised normal distribution. Excess kurtosis was also calculated in order to gain an insight into the exact distribution shape of the data sets; the negative values suggest the data are slightly more spread out than that of a normal distribution, e.g. of platykurtic distribution (Abramowitz and Stegun, 1972) [appendix 7.3].

Depending on the distribution characteristics paired sample t-tests or wilcoxin signed rank tests were performed on each chemical indicator. These tests were performed to determine if there were significant differences between the chemical water quality parameters during November and March. Homogeneity of variance for each of the data sets used in the paired sample t-tests and wilcoxin signed rank tests was confirmed by performing Pitman-Morgan tests. Chemical indicator values between rivers were subjected to independent t-tests or Mann-Whitney U tests to assess whether chemical water quality parameters were significantly different between the two Rivers. Levenes test for equality of variances were run on each data set and where equal variance could not be assumed the unequal variance t-test p-value was reported. Descriptive statistics were reported throughout the analysis and error was calculated as 1 s.d of either the triplicates, sets of triplicates or entire data set.
13

3. Results

3.1 Seasonal changes in chemical health indicator levels on the River Dove and River Tame sites Seasonal variations in NO3- (NO2-)-N, NH4+-N, PO43- -P, pH and dissolved oxygen [DO] on both rivers are displayed in figures 3.1 and 3.2 and are described below.

3.1.1 River Dove

In general seasonal variation on the River Dove [figure 3.1] was characterised by higher levels of NO3- (NO2-)-N and pH in March and higher levels of NH4+-N in November. Conversely DO displayed little temporal change. Concerns regarding the quality of the PO43- -P data meant a comparison between the seasonal data sets was impractical. Depending on the distribution and equality of variance of the data sets [appendix 7.4] paired sample t-tests and Wilcoxin signed rank tests were performed in order to obtain a statistical measure of significant difference. P values below refer to t -tests unless stated.

A.

NO3- (NO2-)-N Figure 3.1a

The mean NO3- (NO2-)-N concentration ( standard deviation) for November (2.21 0.41 mg/L) was far lower than March recordings (3.77 0.49 mg/l) and the data sets were significantly different from one another (p = 0.001, n=18). All 20 equally spaced sample sites displayed higher concentrations of NO3- (NO2-)-N in March and concentrations measured in this month regularly exceeded 4.00 mg/L while November recordings never surpassed 3.00 mg/L.

B.

NH4+-N Figure 3.1b

The mean NH4+-N concentration for November (0.39 0.14 mg/L) was higher than in March (0.21 0.04 mg/L) and the data sets were significantly different from another (p = 0.003, n=20). Despite this statistical significance and in opposition with the mean values some upstream sample sites [AD] displayed lower levels of NH4+-N in November. The spatial trends of figure 3.1 and 3.2 will be further discussed in section 3.2. PO43- -P Figure 3.1c

C.

The mean PO43- -P concentration for November (0.019 0.014 mg/L) was similar to concentrations recorded in March (0.021 0.019mg/L), however the quality of these data sets are questionable [see methods] and it is acknowledged that performing seasonal comparisons and statistical analysis on PO43- -P Dove data would have not been possible.
14

D.

pH Figure 3.1d

The mean pH level for November (7.98 0.12) was lower than the mean level recorded in March (8.36 0.23) and the data sets were significantly different from one another (p = 0.001). All 20 sample sites in March displayed values well above November levels with extreme values exceeding pH 8.4.

E.

Di1ssolved Oxygen Figure 3.1e

The mean DO concentration for November (5.23 0.24 mg/L) was slightly above March (5.11 0.23mg/L). DO data on the Dove was non-normally distributed and Wilcoxin signed ranked tests showed the data sets were not significantly different from one another (p = 0.126, n=18).

3.1.2 River Tame

Seasonal variation on the Rive Tame [figure 3.2] was characterised by higher concentrations of NH4+-N and DO in March and higher concentration of NO3- (NO2-)-N, PO43- -P and pH in November. Seasonal changes in nutrient concentrations [NO3- (NO2-)-N, NH4+-N and PO43- -P] were generally more pronounced than pH and DO.

A.

NO3- (NO2-)-N- Figure 3.2a

The mean NO3- (NO2-)-N concentration for November (11.88 0.81 mg/L) was much higher than in March (8.63 0.69 mg/L) and the data sets were significantly different from one another (p = <0.001, n = 19). All 20 recordings in November exceeded March concentrations by as much as 3.50 mg/L and the highest concentrations surpassed 12.00 mg/L. The lowest recorded March concentration of NO3- (NO2-)-N was below 7.80 mg/L. B. NH4+-N Figure 3.2b

The mean NH4+-N concentration for November (0.28 0.08 mg/L) was far lower than in March (0.51 0.11 mg/L) and the data sets were significantly different from one another (p = <0.001, n=19). All 20 recordings in March were consistently higher than November concentrations and regularly exceeded 0.50 mg/L. Conversely November concentrations did not surpass 0.40 mg/L and at some sample sites fell below 0.2mg/L.

15

C.

PO43- -P- Figure 3.2c

The mean PO43- -P concentration for November (0.79 0.20 mg/L) greatly exceeded the March mean concentration (0.39 0.07 mg/L). The quality control on PO43- -P Tame data was much tighter than that on the Dove data [see methods] and therefore a statistical analysis could be performed, ultimately finding the November data set to be significantly higher than the March data set (p = 0.001, n=20). November concentrations of PO43- -P regularly exceeded 0.80 mg/L while at some sample points March concentrations were as low as 0.20 mg/L.

D.

pH Figure 3.2d

The mean pH level for November (7.44 0.25) was moderately higher than March levels (7.29 0.15) and the data sets were significantly different from one another (p = 0.030, n=20). Despite this March levels were often higher than November recordings at specific sites, however the March data set was characterised by some low values which regularly fell below pH 7.3.

E.

Dissolved Oxygen Figure 3.2e

The mean DO concentration for November (3.23 0.27 mg/L) was a substantial amount lower than mean March concentration (4.97 0.22 mg/L) and the data sets were significantly different from one another (p = 0.001, n=20) when the Wilcoxin signed rank test was performed. All 20 concentrations in March were higher than November values with March concentrations regularly exceeding 5.00 mg/l. November concentrations reached highs of above 4.00 mg/l but values were more consistently around 3.00 mg/l.

3.2. Spatial changes in chemical health indicators along the River Dove and River Tame sites. Spatial changes in NO3- (NO2-)-N, NH4+-N, PO43- -P, pH and DO on both rivers are also represented in figures 3.1 and 3.2. Figure 3.3 further represents this change by displaying moving average [MA] calculations of the chemical health indicators and the key findings on each river are described below. A summary of sample site position can be found in figure 1.1.

3.2.1 River Dove

In general spatial variation on the Dove was characterised by relatively stable concentrations of NO3- (NO2-)-N, increasing levels of NH4+-N, pH and Dissolved Oxygen and highly variable but seemingly trendless concentrations of PO43- -P. These features are described in more detail below.

16

Figure 3.1 [a-e]: Summary chart displaying all the data collected in the study on the River Dove. The five river health indicators are displayed against 20 equally spaced sample sites. Data was collected at two points in the year; November and March and the values are a product of the average of triplicate samples. 1 s.d error margins were calculated on these triplicates and are displayed on the charts.

Fig. 3.2 [a-e]: Summary chart displaying all the data collected in the study on the River Tame. The five river health indicators are displayed against 20 equally spaced sample sites. Data was collected at two points in the year; November and March and the values are a product of the average of triplicate samples. 1 s.d error margins were calculated on these triplicates and are displayed on the charts.

17

A.

NO3- (NO2-)-N Figures 3.1a and 3.3a

Concentrations of NO3- (NO2-)-N remained at relatively consistent through the river course in both November and March months (range = 3.40 0.21 4.20 0.32 mg/L) There are slight variations between the 400m spaced sample sites and M to P were characterised by a gradual increase in concentrations during both months. The MA increased at an average rate of 0.12mg/L/400m between these sites.

B.

NH4+-N Figure 3.1b and 3.3a

Concentrations of NH4+-N increased through the river course during both months. This increase was largely consistent in March with the biggest change occurring between sites F and I where the MA increased from 0.09 0.01 mg/L to 0.018 0.02 mg/L. During November concentrations of NH4+-N were initially very low at sample sites A to D, however the MA increased from 0.07 0.01 mg/L at site C to 0.40 0.05 mg/L by site F. Concentrations after site F were variable but consistently higher than levels recorded at the start of the river course.

C.

PO43- -P Figures 3.1c and 3.3a

Once again due to the low quality controls for the PO43- -P Dove data sets it is hard to address spatial variations; however Figure 3.3a would appear to show negligible variation in the MA (MA range 0.00mg/L/400m 0.01mg/L/400m) through the river course.

D.

pH- Figures 3.1d and 3.3b

pH levels increased through the river course during both months. The increase was principally consistent during November; however March levels displayed the largest increase during sample sites A to C, this change is represented in figure 3.3 where the MA increase by 0.2 pH units between sites B and D.

E.

Dissolved Oxygen Figures 3.1e and 3.3b

DO concentrations increased through the river course during both months however variation between neighbouring sample sites was high. The majority of the increase during November occurred between Sites A-G and K-O where the MA was increasing by an average of 0.1mg/L/400m and 0.15mg/L/400m respectively. During the mid-course of the River November levels of DO decreased slightly. In March DO increased fairly rapidly between sites C and F (0.1mg/L/400m) while the rest of the river course was characterised by a consistent but slow increase.
18

3.2.2 River Tame

Spatial variation on the Tame was characterised by increasing concentrations of NO3- (NO2-)-N and DO, decreasing pH levels and variable or steady concentrations of NH4+-N and PO43- -P. These features are described in more detail below. A. NO3- (NO2-)-N Figures 3.2a and 3.3c

Concentrations of NO3- (NO2-)-N increased through the river course in both November and March. The majority of this increased occurred during the first 10 sites during both months (0.2mg/ L/400m) with concentrations levelling off after this.

B.

NH4+-N Figures 3.2b and 3.3c

Concentrations of NH4+-N were relatively stable through most of the river course during November and March (range 0.15 0.02mg/L 0.31 0.03 mg/L and 0.41 0.05 mg/L 0.61 0.08 mg/L). Some increase occurred at the first few sample sites during November [A-E] where concentrations increased on average by 0.04mg/L/400m. During March concentrations decreased steadily from sites A to E, increased sharply at site F and remained around this concentration (0.48 0.06mg/L) throughout the remaining sample sites. PO43- -P Figures 3.2c and 3.3c

C.

PO43- -P concentration showed opposing spatial trends during November and March. November values were steady from sites A to E before increasing by an average of 0.05mg/L/400m through sites F-L. Concentrations after L were steady. March levels deceased rapidly at an average of 0.08mg/L/400m from A-F before levelling off at 0.31 0.03 mg/L between G-Q. Concentrations then increased rapidly between R-T (0.06mg/L/400m).

D.

pH Figures 3.2d and 3.3d

pH levels decreased sharply through sites A-G at average of 0.03/400m in both November and March. In November levels then remained steady for the remaining sites, however March pH recordings decreased once again between sites L-O (0.05/400m) before increasing to by similar speeds during the following few sample sites.

E.

Dissolved Oxygen Figures 3.2e and 3.3d

DO concentrations increased steadily throughout the whole river course during both November and March at average of 0.03mg/L/400m and 0.06mg/L/400m respectively.
19

Figure 3.3 [a-d]: Simple Moving Averages [SMAs] of the chemical health indicator data for the Tame and Dove during November and March. SMA was calculated using the mean of the sample site value and the values of the sites immediately up and down river of the sample site [SMA = 1 S +S2+S3/3]. Error bars were a product of 1 s.d of the 3x3 triplicate values which contributed to each SMA and were thus calculated from nine pieces of data. The SMAs smooth out any intra-site variance witnessed in figures. 3.1 and 3.2 and provides a general overview of spatial trends.

20

3.3: Inter-river variance

When compared with one another Figures 3.1 and 3.2 display the difference in chemical health indicator levels between the two rivers. Independent t-tests were performed in order to gain a level of statistical significance regarding inter-river variance. The River Tame was characterised by far higher concentrations of NO3- (NO2-)-N and PO43- -P (10.05 0.65mg/L, 0.59 0.07mg/L) when compared to the River Dove (3.01 0.34mg/L, 0.03 0.02 mg/L) (November p = <0.001 and 0.001 respectively; March P = <0.001 and <0.001 respectively), while the Dove displayed higher values of pH and Dissolved Oxygen (November p= 0.002 and 0.001 March P = <0.001 and 0.001 respectively). During November concentrations of NH4+-N were statistically higher on the River Dove (P =0.002) while March concentrations were higher on the Tame (p = 0.020).

3.4: The potential influence of changes in land-use and the implementation of management on chemical health indicator concentrations on the River Tame.

The land use and management maps [Figures 1.2 and 1.3] in Section 1 display the position of current management on the River Tame site and any major changes in land use during its course. Management in the form of purification lakes occurs between sites E-F while an urban to agricultural land use change also occurs between these sites. There are some minor land use changes towards sites R, S and T, however to maintain a relative simplicity the data sets were split in to two groups; Sites A-E and Sites F-T. These groups signify pre and post management data recordings, but also urban and agricultural land use readings. The groupings result in small data sets and rather than rely on inferential statistical techniques to extrapolate from limited data [witnessed in work by Coote and DeHaan (1978)] it was decided statistical analysis would not be used here. This decision was made in light of the added uncertainty small data sets present when performing certain statistical analysis like independent t-tests and the Mann Whitney- U test (Hand et al., 1993). The following sections therefore rely on descriptive statistics and are akin to analysis performed by Garrison (1997).

Figure 3.4 [a-c] presents the nutrient concentration data collected at sites A-E [<management (and land use change)] and F-T [>management (and land use change)] on the River Tame during November and March. In general nutrient levels were somewhat lower at sites A-E than F-T, there were however some exceptions to this trend. Figure 3.4 [d-e] presents pH and DO data under the same groupings and were characterised by lower pH and higher DO concentrations after management and land use change. These trends are described in further detail in the following paragraphs.

21

A.

NO3- (NO2-)-N Figure 3.4a

The mean NO3- (NO2-)-N concentration for < management sites in November and March were 9.42 0.41 mg/L and 8.01 0.31 mg/L respectively. This compares with > management mean concentrations of 11.91 0.76mg/L and 7.82 0.39 mg/L respectively. The Concentrations of NO3 - (NO2-)-N measured in November before management were therefore below concentrations after management, while March concentrations were fairly consistent between both groupings.

B.

NH4+-N Figure 3.4b

Mean NH4+-N concentrations for < management sites in November and March were 0.21 0.07 mg/Land 0.41 0.12mg/L respectively. This compares with > management mean concentrations of 0.33 0.06 mg/L and 0.46 0.11 mg/L. Both months concentrations before management were therefore below concentrations after management, however the upper and lower error margins overlap during < and > management groups. Therefore it is not statistically sound to state that NH4+-N concentrations were different between groupings. C. PO43- -P Figure 3.4c

Mean PO43- -P concentrations for < management sites in November and March were 0.65 0.14 mg/L and 0.64 0.04 mg/L respectively. This compares with > management mean concentrations of 0.81 0.12 mg/L and 0.82 0.11 mg/L. Again the error bars overlap between groupings and therefore variance between them may not be as pronounced as the mean concentrations suggest.

D.

pH Figure 3.4d

Mean pH levels for < management sites in November and March were 7.39 0.13 pH and 7.34 0.11 pH respectively. This compares to > management mean levels of 7.69 0.11 pH and 7.64 0.12 pH. pH was therefore higher after management during both months.

E.

Dissolved Oxygen Figure 3.4e

Mean DO concentrations for < management sites in November and March were 2.88 0.18 mg/l and 4.46 0.24 mg/l respectively. This compares to > management mean concentrations of 3.62 0.31 mg/l and 5.39 0.28 mg/l. DO concentrations were therefore lower before management during both months.

22

23

Figure 3.4 [a-e]: Average NO3- (NO2-)-N, NH4+-N, PO43- -P, pH and DO concentrations taken from triplicate samples across the 20 sample sites on the River Tame during November and March. The data sets are split in to < management (and land use change) [Sites A- E] and > Management (and land use change) [Sites F- T] and are accompanied by 1 s.d error margins which were calculated using the triplicate samples.

3.5: The potential influence of land use changes on chemical health indicator concentrations on the River Dove

The land use maps (figure 1.1) in section 1 display the changes in land use surrounding the River Dove. The major change was deemed to occur between sites E and F. Before site F natural shelterbelt areas like marshland protect the River course from the surrounding agriculture, however from site F onwards this livestock agriculture encroaches on the river and little natural protection is available.
24

Figure 3.5 [a-c] presents the nutrient concentration data collected at sites A-E [<land use change] and F-T [>land use change] on the River Dove during November and March. In general, nutrient levels showed little variation between land use groupings. However, some exceptions to this trend were observed. Figure 3.5 [d-e] presents pH and DO data under the same groupings and were characterised by higher concentrations after land use change. These trends are described in further detail below.

A.

NO3- (NO2-)-N Figure 3.5a

Mean NO3- (NO2-)-N concentrations for < land use sites during November and March were 2.21 0.31 mg/L and 3.75 0.48 mg/L respectively. This compares to > land use concentrations of 2.15 0.28 mg/L and 3.81 0.41 mg/L. NO3- (NO2-)-N concentrations therefore varied very little between land use groupings.

B.

NH4+-N Figure 3.5b

Mean NH4+-N concentrations for < land use sites during November and March were 0.10 0.01 mg/L and 0.12 0.01 mg/L respectively. This compares to > land use mean concentrations of 0.33 0.06 mg/L and 0.22 0.02 mg/L. Concentrations were therefore much lower during sites A-E before land use changes. PO43- -P Figure 3.5c

C.

Mean PO43- -P concentrations for < land use sites during November and March were 0.02 0.01 mg/L and 0.02 0.01 mg/ L respectively. This compares to > land use mean concentrations of 0.02 0.01mg/L and 0.02 0.01 mg/L. Concentrations therefore varied very little between land use groupings. Once again PO43- -P Dove data has to be approached with caution because of the controls on the data inclusion [see methods]. The high error margins displayed on the group means is indicative of weak data.

D.

pH Figure 3.5d

Mean pH levels for < land use sites during November and March were 7.67 0.12 and 8.23 0.09 respectively. This compares to > land use mean levels of 8.01 0.13 and 8.29 0.11. pH before land use change in November is clearly much lower than levels recorded after land use, however March recordings show little variation between groupings.

25

E.

Dissolved Oxygen Figure 3.5e

Mean DO concentrations for < land use sites during November and March were 3.94 0.26 mg/L and 3.98 0.31 mg/L respectively. This compares to > land use mean concentrations of 5.16 0.42 mg/L and 4.31 0.29 mg/L. DO concentrations were before land use change were lower than recordings after land use, however November concentration differences were more pronounced.

26

Figure 3.5 [a-e]: Average NO3- (NO2-)-N, NH4+-N, PO43- -P, pH and DO concentrations taken from triplicate samples across the 20 sample sites on the River Dove during November and March. The data sets are split in to < land use change [Sites A- E] and > land use change [Sites F- T] and are accompanied by 1 s.d error margins which were calculated using the triplicate samples.

3.6: The potential influence of management on chemical health indicator concentrations on the River Dove

The Management maps [Figure 1.3] in section 1 display the positions of weir management on the River Dove. A total of seven weirs were present during the Dove section, the first of which occurred after site F, from there six more weirs occurred at regular intervals until site P, whereby no further weirs were present. The five chemical health indicator data sets were divided into two groups; sites after weir management and sites with no management.

27

Figure 3.6 [a-e] displays histograms of the NO3- (NO2-)-N, NH4+-N, PO43- -P, pH and Dissolved Oxygen data sets divided in to these two groups for November and March months. Groupings were generally characterised by similar medians, however values at non-managed sites appeared to have significantly larger ranges than those at weir managed sites.

A.

NO3- (NO2-)-N Figure 3.6a

There would appear to be lower concentrations of NO3- (NO2-)-N at non-managed [NM] sample points than there are at weir managed [WM] sites during November. Conversely during March figure 10 would appear to show higher NO3- (NO2-)-N concentrations at NM sample points. The WM histograms for both November and March display a much tighter range of concentrations; however this could be a product of the fewer data values available for analysis at WM sites.

B.

NH4+-N Figure 3.6b

Higher concentrations of NH4+-N are displayed at WM sites in November. The median value (0.42 mg/L) is well above the median of NM sites (0.25 mg/L). March concentrations at WM and NM sites are fairly similar and there are no obvious differences between the two groupings. PO43- -P Figure 3.6c

C.

Figure 3.6c would suggest there are slightly higher concentrations of PO43- -P at WM sites during both November and March.

D.

pH Figure 3.6d

pH levels differed only slightly when comparing the median values of WM and NM sites during November (7.91 and 7.82) and March (8.34 and 8.36), however the range of values at NM sites was substantially wider than at NM site suggesting all extreme values occurred during stretched of the river where no management was present.

E.

Dissolved Oxygen Figure 3.6e

DO concentrations were higher at NM sites during both months; however the March NM data set was also characterised by a larger majority of low concentrations suggesting high variability within the data set.

28

e
Figure 3.6 [a-e]: Box and whisker charts displaying NO3- (NO2-)-N, NH4+-N, PO43- -P, pH and Dissolved Oxygen concentrations on the River Dove during the two sample periods for the seven sites directly after rock weir management and the thirteen sites where no management was present. Data was collected within 50 metres down river of weir location at the managed sites while the non-managed sites were more than 400 metres from any management. Values are a product of average Concentrations taken from triplicate samples.

29

4. Discussion

The results of this study provide insights into the chemical health of two rivers in the Trent catchment; the River Dove and the River Tame. The rivers are characterised by differing surrounding land use practices and opposing levels of management intensity. The study attempted to assess how these differences influenced the chemical health of each river and to understand if these changes affected seasonal variation. The following discussion will address these issues in relation to each of the five chemical health indicators measured [NO3- (NO2-)-N, NH4+-N, PO43- -P, pH and dissolved oxygen] and ultimately attempt to suggest how management could be improved or implemented in the future. Before doing this it is necessary to define healthy levels of each indicator as suggested by various environmental bodies and to compare these to the concentrations measured at each river.

4.1. Measured concentrations and acceptable chemical health

A.

NO3- (NO2-)-N

The European Environment Agency [EEA] assert that concentrations of NO3- (NO2-)-N below 0.3mg/L can be classed as natural background levels. Concentrations above 0.3mg/L are considered to be anthropogenically derived and anything exceeding 7.5mg/L is classed as poor quality (EEA, 2012) Further to this concentrations above 5.6mg/L are deemed unsafe to consume under the Surface Water for Drinking Directive (EU, 1975). Concentrations of NO3- (NO2-)-N on the Dove did not exceed either guideline while Tame concentrations surpassed 7.5mg/L at all twenty sample sites during both months of testing.

B.

NH4+-N

Higher Ionized Ammonium concentrations do not necessarily indicate an unhealthy river due to the relationship between pH, temperature and NH3. Under High temperature and pH conditions it is possible lower concentrations of NH4+-N indicate a more unhealthy state because the conditions are facilitating the conversation of NH4+-N to NH3 -N, which is considered to be more toxic to the ecosystem (Knight et al., 2000). Throughout the discussion the USEPA (1987) guideline table for inferring NH3 N concentration from NH4+-N, pH and temperature levels will be used [appendix 7.5] in order assess health. The USEPA (1987) recommends a limit of 0.02mg/L of NH3 N in freshwater ecosystems. Maximum concentrations of NH4+-N on the Dove reached 0.7mg/L in November, this equates to 0.01mg/L of NH3 N under average November pH and temperature conditions and therefore the Dove can be considered healthy in terms of its ammonium concentrations.

30

Concentrations on the Tame reached similar highs however the rivers lower average pH will slow the conversation of NH4+-N to NH3 N and therefore it can also be considered healthy. C. PO43- -P

The EEA consider concentrations of PO43- -P below 0.01mg/L to be natural background levels. Concentrations above 0.01mg/L are considered to be anthropogenically derived (EEA, 2012) and the UK Environment Agency [EA] regards anything above 0.1mg/L as high (EA, 2012). PO43- -P concentration on the Dove never exceeded the EA guidelines while Tame concentrations were regularly between four and seven times higher than 0.1mg/L

D.

pH

The Water Framework Directive states that rivers in England displaying pH levels of between 6 and 9 are to be considered of high or good quality (WFD, 2008). pH levels on both rivers were well inside these guidelines.

E.

Dissolved oxygen

The WFD provide DO guideline levels for freshwater ecosystems in percent saturation. Percent saturation is a product of DO (mg/L), temperature and altitude. Average temperatures of the rivers were obtained after the study via the Centre for Ecology and Hydrology (2012). These temperatures, along with the mg/L recordings, were cross-referenced against a simple DO saturation calculator chart [figure 4.1] and provided the study with accurate % saturation DO levels for each integer concentration value [Table 4.1]. Altitude change was discounted because studies have shown it has negligible impact upon DO concentration [4%/300m] (Bagalwa, 2010). The WFD states rivers displaying percent saturation levels of DO between 60 and 75 are of good quality (WFD, 2008). Both rivers fall short of these guidelines with concentration of DO on the Dove ranging from 46mg/L (39-57% saturation) while DO on the Tame ranged from 3-6mg/L (36-57%) during both months.

4.2 Controls on water quality

4.2.1 Seasonality

The results of this study show a clear seasonal variation between most of the chemical health indicators on both rivers. The following text outlines the magnitude of this variation and uses literature to speculate upon the most likely causes.
31

DO (mg/L)

Tame and Dove 10C November - % saturation

Tame and Dove - 15C March - % saturation

3 4 5 6 7

36 39 43 52 73

38 41 46 57 79

Figure 4.1: % Saturation levels of Dissolved Oxygen were calculated from recorded values (WOW, 2012).

Table 4.1: % saturation Dissolved Oxygen calculated from recorded levels in mg/L and average November and March water temperatures (CEH, 2012). There was a slight variation in temperatures between the two rivers in November [0.8C] and March [0.5C], however these small differences have negligible impacts on % saturation and therefore the two rivers have been grouped in to seasonal temperature

A.

Nitrification processes

Concentrations of NO3- (NO2-)-N on the Dove in March (x 3.81 mg/L) were consistently double the values recorded in November (x 2.13 mg/L, p = 0.001) and the magnitude of this change could be explained by a reduction in denitrification. Christensen et al. (1990) find in their study that when spring conditions facilitate benthic algal photosynthesis the resulting increase in O2 production causes denitrification to be reduced by up to 85%. Potentially higher algal levels in March may also promote increased NH4+-N uptake (Fujita, 1985), which could partially explain the lower concentrations of NH4+-N (Nov - x 0.39 mg/L, March - x 0.21 mg/L, p = 0.003) recorded in this month. Concentrations of NO3- (NO2-)-N and NH4+-N on the Tame showed opposing seasonal variation to that witnessed on the Dove with NO3- (NO2-)-N significantly higher in November (x 11.81 mg/L compared to x 8.45 mg/L, p = < 0.001) and NH4+-N higher in March (x 0.48 mg/L compared to x 0.31 mg/L, p = < 0.001). It is possible that wetter March conditions facilitated the leaching of NH4+-N from urban zones to the river course (Heathwaite and Jones, 1996). B. Agricultural practice and climate variation

Temporal variation in NO3- (NO2-)-N and PO43- -P concentrations have been shown to be heavily influenced by seasonal alterations in fertiliser application (Chen et al, 2005; Casey et al., 2006) and it is likely this contributed towards the variation displayed on both rivers. It could be expected that seasonal variation of pH would be more pronounced on the Tame due to fluctuations in nitrogen oxide inputs from industrial processes (Reid, Macloed and Cresser, 1981) in urban land use zones; however this is not the case. pH on the Tame varied slightly seasonally (Nov - x 7.44 , March - x 7.29, p = 0.030) while Dove levels showed large deviation ( x 7.98, x 8.36, p = < 0.001). This
32

deviation could be in part due to the origins of the river flow. Howland et al. (2000) hypothesise that in dry conditions groundwater flow is the dominating water origin and hence the river becomes rich in weathered bedrock ions which actively raise the pH. It is possible this theory could be applied to the Dove results as the majority of March precipitation was locked up in snow and the bulk of the flow witnessed was probably groundwater based. In contrast, urban land use on the Tame may have the potential to nullify seasonal variations in groundwater and surficial flows due to impermeable surface presence, hence dulling variation in pH levels. DO concentrations varied between seasons on the Tame (x 3.23, x 4.97, p = 0.001) and the majority of literature suggest these fluctuations are a response to changes in flow dynamics and temperature (Gausch et al., 1998).

4.2.2 Land use

The results of the study appear to show a relationship between type of land use and most indicator concentrations. The following text assesses the strength of these relationships by comparing data collected in this study with the findings of previous work. NO3- (NO2-)-N, NH4+-N and PO43- -P

A,

There is a clear difference in nutrient concentrations both between rivers and spatially along each study section. Previous studies have heavily suggested that surrounding land use has a large impact upon concentrations of NO3- (NO2-)-N, NH4+-N and PO43- -P within a fluvial ecosystem (Haygard and Jarvis, 1997). Ahearn et al. (2005) assert in their study that agricultural practices contribute more NO3- (NO2-)-N and PO43- -P to river courses than any other land use, with urban contributions negligible in comparison. The theory is reinforced in this study by the significantly lower concentrations of NO3- (NO2-)-N and PO43- -P ( x 8.71 mg/L and x 0.64mg/L compared to x 9.92 mg/L and x 0.82mg/L) before agricultural land use on the River Tame [Figure 3.4]. However far lower concentrations of NO3- (NO2-)-N and PO43- -P throughout the Dove would suggest nutrient pollutant levels are more intrinsically linked to the type and intensity of agricultural practice than the sheer presence of farming. Work by Ongley (1996) states that irrigated arable land has the potential to cause high riverine levels of NO3- (NO2-)-N via efficient fertiliser run off and soil particle entry and therefore high concentrations on the Tame are likely a response to the irrigated arable practices which line its banks. Inter River differences in PO43- -P concentrations (Tame - x 0.73 mg/L; Dove - x 0.02 mg/L) reported in this study oppose findings in previous work. It has been suggested by Edwards and Withers (2007) that there are disproportionate P-surpluses between livestock [20kg/ha] and arable farming [10kg/ha] practices and therefore PO43- -P concentration are expected to be highest in rivers

33

surrounded by livestock agriculture [e.g. the Dove]. The lower PO43- -P values on the Dove could be a response to the lack of feed crop farming based in the immediate vicinity (PDNPA, 2012). Hooda et al. (2000) suggest that the majority of P-surpluses and resultant run-off problems within livestock farming are based around the growth of animal feed, while Bosch et al. (2006) outline the diminishing pollutant effect of manure spreading at varying distances from the river course.

NH4+-N Concentrations, which displayed little spatial variation on the Tame (before land use/ management - x 0.31mg/L compared to after - x 0.36mg/L), could be explained by a combination of land use and nitrification drivers. Sewage leakage and effluence are the likely causes of NH4+N in the urban land use zone on the Tame. Studies by Paul and Mayer (2001) and Whipple and Hunter (1974) suggest that concentrations in this region would be higher than those in agricultural areas. However Curtis et al. (1975) show that where the Tame is slow due to channel widening (EA, 2012) sedimentation build up facilities the nitrification of NH4+-N in to NO2- N due to the successful harbouring of nitrifying bacteria, actively lowering concentrations of NH4+-N. In agricultural zones a steady but relatively lower rate of NH4+-N polluting will occur due to commercial fertiliser runoff (Puckett, 1995), however this NH4+- will be less exposed to nitrification n due to the lower sedimentation levels. This process would actively increase concentrations of NO3- (NO2)-N in the urban land use zone. It is therefore likely agricultural land use is an even larger driver towards NO3- (NO2-)-N pollution than first thought as the potential gap is nullified by disproportionate nitrification processes. On the Dove NH4+-N concentrations increased by significant amounts (x 0.28mg/L compared to x 0.11mg/L) where livestock agriculture infringed upon the boundaries of the river course. At sample sites where land cover like wetlands provided the river with natural protection NH4+-N concentrations were minimal. Saunders and Kalff (1999) performed studies on wetlands finding riverine concentrations of nitrogen reduced due to retention, denitrification and aquatic uptake in the wetland area.

B.

pH and dissolved oxygen

DO and pH levels were higher on the river Dove at sites where no natural land cover protection was present (x 4.62 mg/L and x 8.14 compared to x 3.96mg/L and x 7.89) Xh et al. (2007) propose that increasing concentrations of NO3- (NO2-)-N, NH4+-N and PO43- -P in a freshwater ecosystem causes the pH of the water to become acidic as the higher nutrient levels amplify macrophyte growth and therefore increased cellular respiration. This is contrary to the findings on the Dove where pH became more alkaline as nutrient levels increased. It would therefore appear land use is having little impact on pH levels on the Dove and any spatial variation is likely a response to natural changes in local lithology (Walling and Webb, 1974). The facilitation of macrophyte growth via increased nutrients levels should have theoretically correlated with decreased DO concentration due to in-water respiration increases (Caraco and Cole, 2002). However Brussard and Reigman
34

(1998) suggest concentrations of PO43- -P exceeding 0.1mg/L are needed to promote large scale macrophyte growth and therefore it would appear nutrient levels were not pronounced enough to facilitate respiration increases. Spatial variation in DO is consequently likely to be a result of small changes in flow dynamics (Papagiorigio, 2012). Sample sites surrounded by urban land on the Tame were characterised by significantly lower pH (x 7.36 compared to x 7.67) levels but higher DO concentrations (x 3.61 mg/L compare to x 4.42mg/L). Vega et al. (1998) conclude in their study variations in mineral composition and pH levels in polluted waterways are largely governed by temporal and spatial changes in weather and lithology rather than anthropogenically driven factors. It would seem likely this is also the case in this study.

4.2.3. Management

A.

Purification lakes on the River Tame

Rofe (1994) states that the purification lakes on the River Tame are of little or no use in light of modern sewerage systems and the findings of this study appear to concur with Rofes viewpoint. The majority of the nutrient health indicators tested for in this study increased to concentrations above EEA, EA and WFD guidelines after management. There is sufficient evidence to suggest that modern day nutrient concentrations in the Tame are not abundant enough to flocculate and settle into the benthic sediment of the purification lakes; instead the lakes allow for the suspension of the nutrients in the water column (Batty and Hallberg, 2010). The decreased flow rates in the lakes may even be facilitating ammonification conditions via sedimentation and denitrifying bacteria increases (Curtis et al. 1975), thus decreasing the chemical health of the river course by increasing NH4+-N concentrations. Using appendix 7.5 it is possible to calculate toxic levels of NH3-N from the recorded levels of NH4+-N; concentrations of NH3-N were approximately 1% of NH4+-N in March and 0.6% in November in response to pH and temperature averages. This equates to <0.02mg/L concentrations of NH3-N during both months, which is below the threshold guidelines set by the USEPA [see section 4.1]. Therefore while the lakes may be facilitating NH4+-N build up, it is unlikely this increase is causing any harm to the ecosystem. Evidence from Rofes work and this study appear to suggest that since the creation of the lakes in 1982 there has been a shift in the influence of types of land use upon the chemical health of the Tame. Presently agricultural land appears to be affecting nutrient levels within the water course to a greater extent than urban land, indicating the purification lakes are both outdated and misplaced.

B.

Weir Management on the River Dove

Management on the section of the River Dove was restricted to seven unobtrusive rock weirs (PDNPA, 2012) designed to enhance trout fishing conditions by encouraging faster flow and
35

higher DO concentrations. Sample sites near weir-management [WM] displayed nearly double the median concentration of NH4+-N (0.42 mg/L) than sites > 400 metres from away from management [NM] (0.25mg/L). This in part could be due to the increased variation in DO concentration on NM sites (3.00-7.00 mg/L). At WM sites the weir construction was facilitating more consistent conditions in regards to flow dynamics and was probably helping enhance consistent DO conditions (3.40-5.20 mg/L) (Papagiorigio, 2012). At NM sites DO levels were exposed to natural flow dynamics; it is possible where natural flow and aeration were increased the resultant high aerobic conditions were facilitating nitrification, thus decreasing NH4+-N (Richardson et al., 2011) All indicators levels were characterised by a more consistent range at WM sites and it is likely the management was limiting natural variation drivers. Chemical indicator concentrations consistently were at healthy levels and fell below the stipulated guidelines [section 4.1] at both WM and NM sites with the exception of DO. Where DO was below 6mg/L it fell short of the 65-80% saturation guidelines set by the WFD [see table 4.1].

4.3. Management recommendations

4.3.1 River Tame

Concentrations of chemical water quality parameters on the Tame fall short of many of the chemical guidelines set by the EEA, EA and WFD. NO3- (NO2-)-N and PO43- -P concentrations were well above healthy levels [section 4.1] and DO % saturation was consistently below the 65% WFD guidelines. Therefore the purification lake management appears redundant and it is likely nutrient levels will remain high unless pollution from agricultural land is combated. Combating the nutrient pollution impact of agricultural land on the Tame could be approached in two ways; limiting fertiliser use and controlling entry of fertiliser to the water course. Wilthers and Lord (2002) suggest fertiliser use on arable land in the UK continuously exceed production requirements, therefore ensuring farmers use the correct amount of fertiliser would undoubtedly limit pollution of the river. This problem has been occurring globally for years however, and it is unlikely to be solved on a micro-scale. Controlling fertiliser entry to the water course would appear a more efficient and practical management scheme. This study showed natural land cover like wetland limited the entry of nutrients to the River Dove and the creation of wetland near the River Tame could vastly reduce NO3- (NO2-)-N, NH4+-N and PO43- -P concentrations in the water course via retention, denitrification and aquatic uptake (Saunder and Kiff, 1999).

4.3.2.River Dove

Concentrations of the majority of chemical water quality parameters on the Dove were well inside the chemical guidelines set by the EEA and WFD [section 4.1]. At times NH4+-N concentrations
36

increased to levels which would infer toxic NH3 concentrations of around 0.01mg/L, however these levels remain under the 0.02mg/L standards set by the USEPA. DO levels often fell short of the 65% saturation WFD standard, and any future management should attempt to encourage higher DO concentrations. Management should therefore focus around increasing aeration rates. Although the correlation between weir use and DO concentrations was low in this study previous work has shown intense weir management can increase aeration rates and DO levels (Wahl , Young and Miller, 1994). It possible the construction of larger weirs on the Dove may help to improve chemical water quality.

4.4 Limitations of the study

Natural drivers of chemical water quality make assessing anthropogenic influences like land use difficult. Previous studies have shown weather and lithology variations can impact upon background concentrations of nutrients and pH levels, influencing both spatial and temporal changes in their abundance (Walling and Webb, 1974). Although background levels of NO3- (NO2-)-N, NH4+N and PO43- -P [see section 4.1] are likely to be very low future studies may wish to calculate these in order to define precise anthropogenic inputs. Furthermore, while spatial variation in the river was accounted for via equal distance sample sites it is difficult to assess the influence of a particular land use on downstream sites. Therefore it is possible pollution via urban areas on the Tame was making agricultural pollution seem more pronounced. The study was limited to a small section of each river due to logistical and time constraints and future work should try and focus on the whole river course. This should provide a more reliable indication of the relationship between land use and chemical water quality. There were also some limitations with the analysis of the nutrient sample; principally the AA3 was unable to detect the small amounts of PO43- -P on the River Dove. 5. Conclusions

The work performed in this study provides detailed information regarding the influence of changing land uses upon concentrations of NO3- (NO2-)-N, NH4+-N, PO43- -P, pH and dissolved oxygen within a riverine system. It is concluded that arable land use has the largest potential to impact upon overall chemical water quality, while livestock agriculture and urban land use contribute towards higher concentrations NH4+-N. Additionally previous studies have suggested in-river processes related to macrophyte and bacteria growth are likely influencing pollutant concentrations and therefore may be masking the true magnitude of land uses control on chemical water quality. The work further suggests that current management on the River Tame is failing to control any of the parameter concentrations, resulting in a river high in pollutants. Conversely the River Dove is low in anthropogenic sourced nutrient inputs and in a relatively healthy state. Natural land cover would

37

appear to be protecting the main water body from some agricultural nutrient pollutants; however current management is failing to address low DO concentrations. Future work should therefore focus on establishing appropriate and correctly placed management strategies on the River Tame.
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7. Appendices

Run 1 2 3 4 5 6 7 8

NH4+-N 0.9982 0.9987 0.9988 0.9981 0.9950 0.9966 0.9964 0.9971

NO3- (NO2-)-N 0.9996 0.9999 0.9997 0.9997 0.9968 0.9969 0.9967 0.9967

PO43- -P 1.000 0.9996 0.9996 0.9996 0.9999 0.9962 0.9957 0.9964

Appendix 7.1: Correlation coefficient values for NO3- (NO2-) - N, NH4+-N and PO43- -P standards during each run of the AA3. Values were consistently above 0.995 (NH4+-N), 0.996 (NO3- (NO2-) N) and 0.995 (PO43- -P).

Data point excluded November Tame - NH4+-N - Sample B March Tame - NH4+-N Sample L March Dove NH4+-N Sample L November Dove NO3- (NO2-) - N Sample A November Dove NO3- (NO2-) - N Sample S November Dove PO43- -P Sample C November Dove PO43- -P Sample P March Dove pH Sample A March Dove DO Sample A March Dove DO Sample D March Tame NO3- (NO2-) - N Sample K

RSD value too high?

Statistical outlier?

Appendix 7.2: Full list of excluded data. Data was excluded for either displaying an %RSD value of above 30* or being highlighted as a statistical outlier within the statistical software package SPSS. *Note: PO43- -P data displaying %RSD values above 30 were included [see section 2.5].

43

Appendix 7.3: Distributions characteristics of each data set. Sharipo-wilks values < 0.05 were considered non-normally distributed while the small negative kurtosis values suggested the data was relatively normally distributed but characterised by some extreme values. The distributions of each data set influenced which statistical tests were performed during section 3 [see section 2.6]

Paired sample t-test

Wilcoxin signed rank

Statistically significant difference?

Dove Nitrate Dove Ammonium Dove Phosphate Dove pH Dove DO Tame Nitrate Tame Ammonium Tame Phosphate Tame pH Tame - DO

0.001 0.003 0.921 0.001 N/A 0.001 N/A 0.001 0.030 N/A

N/A N/A N/A N/A 0.126 N/A 0.001 N/A N/A 0.001

Appendix 7.4: Depending on the distributions of the data sets [appendix 2.3] either paired sample t-tests or Wilcoxin signed ranked tests were performed in order to assess seasonal change. Values in the table refer to the p-values of the tests performed between seasonal data on each indicator. Values < 0.05 were deemed to mean the data were significantly different from one another. Pitman-Morgan tests confirmed equal variance between the parameters. 44

Temp C 5 10 15 20 25 30

pH 6.0 0.013 0.019 0.027 0.040 0.057 0.080 6.5 0.040 0.059 0.087 0.13 0.18 0.25 7.0 0.12 0.19 0.027 0.40 0.57 0.80 7.5 0.39 0.59 0.86 1.2 1.8 2.5 8.0 1.2 1.8 2.7 3.8 5.4 7.5 8.5 3.8 5.6 8.0 11 15 20 9.0 11 16 21 28 36 45 9.5 28 37 46 56 64 72

Appendix 7.5: Percent total ammonia present in the toxic, un-ionized ammonia form in a zero salinity solution (USEPA, 1987). NH3-N was calculated using this table from recorded concentrations of NH4+-N.

45