Report - Nenthead

Oliver Ben Field
130074056
CEG3603 Research Methods in Environmental Pollution
1
Water analysis report on Nent River, to
assess the impact on Nenthead Lead
and Zinc abandoned mine. Nenthead,
Cumbria.
Author – Oliver Ben Field
Abstract:
It is widely known that water quality is greatly affected by close proximity mining activity. Investigation
into the River Nent, Nenthead in an Area of Outstanding Natural Beauty and UK’s North Pennines
Orefield covering an area of 25km2, Cumbria, on the Alston moor. They mined Lead (Pb) and Zinc (Zn)
ore during the 17th and 19th century (Nuttall and Younger, 2015). During this study the Cation and Anion
concentration that were collected along the River Nent were prepared in the laboratory and analysed
further using Atomic Absorption Spectroscopy (AAS) for the Cations and Ion-Chromatography (IC) for
the Anions. Results showed that certain ion were significantly higher leaving the mine compared to the
concentration entering the mine site (Zn, Mg), others on the hand did not (Pb, PO4). The accuracy and
precision of our results were fairly negligible apart from a few ions, such as Zn and Mg, however only a
few results were under 10, thus predominately negligible and not recording the true concentrations in the
sample. This study provides an insight to the effect that the abandoned mine had on the water quality of the
River Nent, which could be related to sites of a similar nature.

Student number - B3007405
2
Table of Contents
1: Introduction .............................................................................................................................................4
1.1.1 – background information.....................................................................................................................5
1.2 – Study Location......................................................................................................................................5
1.3 – Aims and expected outcomes ...............................................................................................................5
2.1- Methodology..........................................................................................................................................6
2.1.1– Step 1 – Select Equipment in field .....................................................................................................6
2.1.2 – Step 2 – Data collection.....................................................................................................................6
2.1.3 - Sample site locations:.........................................................................................................................6
2.1.4 - Site description:..................................................................................................................................6
2.2 - Analytic methods:..................................................................................................................................7
2.2.1 - Alkalinity: .......................................................................................................................................7
2.2.2 - Analysis of major and trace Cations and Anions:..........................................................................7
Storage:..........................................................................................................................................................8
2.2.3 – Anion analysis: ..............................................................................................................................8
2.2.4 – Cation analysis: ...........................................................................................................................10
Atomic absorption spectroscopy (AAS) was carried out for our further analysis. AAS measures the
intensity of the light absorbed when photon move from ground state to excited state shown in figure 8. .11
2.3 - Calculations of raw data:.....................................................................................................................13
3.1 – Cation and Anion results..................................................................................................................13
3.1.1 –Cation analysis..................................................................................................................................13
Lower Limit of Detection (LLD):................................................................................................................13
3.1.2 - Sodium (Na): ................................................................................................................................14
3.1.3 – Potassium (K):.............................................................................................................................15
3.1.4 - Calcium (Ca) ................................................................................................................................15
3.1.6 – Lead (Pb) .....................................................................................................................................17
3.1.7 – Zinc (Zn) ......................................................................................................................................18
3.2.1 –Anions Analysis................................................................................................................................18
2.2.3 - Chloride (Cl) ................................................................................................................................20
3.2.4 - Nitrate (NO3) ...............................................................................................................................20
3.2.5 – Sulphate (SO4).............................................................................................................................21
3.2.7 – Phosphate (PO4) .........................................................................................................................21
3.2.8 – Alkalinity (HCO3)........................................................................................................................22
3.3 – Charge balance calculations ...............................................................................................................23
3.4 – Precision: ............................................................................................................................................24
3.5 – Accuracy:............................................................................................................................................25
3.6 – other essential recordings ...................................................................................................................26
3.5 – piper diagram......................................................................................................................................27
4.1 Discussion.............................................................................................................................................27
4.1 Overview: ..............................................................................................................................................27
4.2. Macronutrients:.....................................................................................................................................28
Cations:....................................................................................................................................................28
Sodium and Potassium: ...........................................................................................................................28
Magnesium and Calcium:........................................................................................................................28
Anions:.....................................................................................................................................................28
4.3 - Micronutrients: ....................................................................................................................................29
Cations.....................................................................................................................................................29
4.5 - Charge balance: ...................................................................................................................................29
4.6 -Accuracy and precision ........................................................................................................................29
4.7 - In field results:.....................................................................................................................................29

Oliver Ben Field
130074056
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5 - Conclusion.............................................................................................................................................29
6 - Limitations ............................................................................................................................................29
7 - Acknowledgements...............................................................................................................................30
8 - References .............................................................................................................................................30
9 – Appendices............................................................................................................................................35
Appendix 1: Background information of the ore formation........................................................................35
Appendix 2: affect of Pb on environmental and health risk ........................................................................38
Appendix 3: Heavy metal toxicity and effect on fish..................................................................................39
Appendix 4: Colorometry and Autoanalyser further description ................................................................40
Appendix 5: holding times...........................................................................................................................41
Appendix 6: A graph of our results with volume of acid on the x axis against the pH on the y axis .........42
Appendix 7: calibration standards for Anions .............................................................................................43
Appendix 8: calculations .............................................................................................................................44
Appendix 9: Description on anions and Cations in waterways ...................................................................45
Appendix 10: Planks equation (AAS) .........................................................................................................49
Appendix 11: AAS advantages and disadvantages .....................................................................................50
Appendix 12 – Reasons why used specific settings for Ion chromatography.............................................51
Appendix 12 – Limestone formation - Nenthead ........................................................................................52
Appendix 14: calibration curves..................................................................................................................53

4
1: Introduction
The North Pennines is famous for veins of lead (Pb), Zinc (Zn) and fluoride (F) formed ~290 MA by
hydrothermal process initiated by the Weardale granite (see appendix 1) (Global Geoparks Network,
North Pennines, 2015). This lead to Pb and Zn mining in close proximity to the river Nent, which causes
critical changes in the aquatic chemical composition, such as elevated toxic metals from weathering of
exposed ores (Gajoweic and Witkowski, 2015).
High concentrations of toxic micronutrients have multiple affects on the aquatic systems J. A. B. Bass
(2008) as part of the Environmental Agency concluded that toxic metals reduce species numbers of both
macroinvertebrates and diatoms in the field, this can provide an effective and sensitive tool for detecting
metal toxicity. The Toxicity Binding Model (TBM) provides clear toxicity thresholds of specific flora and
fauna identified (see appendix 2 and 3).
The river Nent occupies five mine water discharges shown in Figure 1. These are point sources of
pollution, however river sediments, bank deposits and tailings material represent diffuse metal
contamination occurring along the length of the river (Nuttall and Younger, 2015).
Figure 1: Map of the Ninth Valley showing the main inputs of metal contamination (Nuttall and
Younger, 2015).

Oliver Ben Field
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1.1.1: Background information
The underlying geology of the Nenthead catchment area is predominately limestone and till in with the
lower catchment, whilst firestone sandstone and Stainmore formation (clay to gravel) occupy the upper
catchment.
1.2: Study Location NY784434
Nenthead is located in an Area of Outstanding Natural Beauty for rare lichens and specific species of
plant that grow on the metal-rich dumps, the valley being of a ‘National Ancient Monument’
(Nentheadmines.com, 2015). It lies 1,500 feet above sea level in close proximity to the river Nent
(Cumbria RIGS, 1992).
1.3: Aims and expectedoutcomes
Aims:
Analyse the River Nent anion and cation concentration from the base line flow of the river compared to
the concentration leaving the mine.
Expected outcomes:
Hoping to find multiple correlations because of the Pb and Zn mining activity via mine water discharge
and an increase in toxic Anions and Cations leaving the mine in comparison to the base line flow.
Firestone sandstone
Limestone
Till
Stainmore formation
Site location
Figure 2: A map to show the underlying geology in the catchment area of
the River Nent (Digimap.edina.ac.uk, 2016)
Start
Finish
Site 1
Site 2
Site 3
Site 4
Key:

6
Sample point
Key:
Site 1
Site 2
Site 3
Site 4
2.1: Methodology
2.1.1: Select Equipment in field
 0.45 micron filter
 Cation containers contained nitric acid to lower the pH
 Hatch alkalinity test kit
 Infield titration for alkalinity, adding sulphuric acid into the solution in situ with a bromocreasol
methyl red indicator
 Multiparameter water quality probe
2.1.2 – Step 2 – Data collection
We used judgemental sampling based on a professional knowledge on what sites would be best to sample
for the greatest difference in ion concentration between sites. This discounts biased because we stated
reasons why each site was chosen (section 2.1.3).
At every site location we had four pre-washed polypropylene bottles. Two for Anion collection and two
for Cation collection contains nitric acid to lower the pH to prevents the Cations from precipitating out of
solution. We filled the bottle to the rim, which prevents ions becoming volatile. Polypropylene bottles
were used instead of glass containers because trace metals strongly absorbed onto the walls of the glass
container as well as brittle and heavy (Corning, 2008). During collection we stud downstream of the
collection site shown in figure 3 to prevent sample contamination. We then filtered them through a 0.45-
micron filter to remove the particular matter.
To measure alkalinity we used a hatch alkalinity test kit with a bromocresol methyl red indicator mixed
into the sample. Then titrated dilute hydrochloric acid into the solution until the colour turned grey, which
meant the solutions pH was 4.5. We recorded the volume of hydrochloric acid titrated, the more alkaline
the sample the more acid was used. We also recorded, Conductivity, Oxidation-reduction potential (EH),
Total Dissolved Solids (TDS) and Temperature with Myron L Ultrameter II 6P, which was calibrated
prior to each sampling event.
2.1.3 - Sample site locations:
2.1.4 - Site description:
Start
Finish

Oliver Ben Field
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2.2 - Analytic methods:
2.2.1 - Alkalinity:
Alkalinity was analysed within a week to maximise accuracy by ensuring analysis was well within the
holding time of 14 days. Then standardised the hydrochloric (HCl) acid to an exact concentration to
optimise accuracy and precision, the average concentration of HCl was 0.1028 m/L with a % Stdev of
2.9% after the four repeats. The acid was then diluted by a factor of 10 for precision and accuracy.
Lastly, we titrated 5ml of dilute acid at a time into the sample (25ml), whilst recording the pH until it
reached 3, the results were plotted on a graph (see appendix 6).
2.2.2 - Analysis of major and trace Cations and Anions:
In the laboratory we multiplied our samples by 4 (figure 4) to allow an increased number of repeats,
which improves reliability as anomalies done skew the data as significantly.
1
1A
1A1
1B2
1B1
1A2
1B
Figure 4: This shows how we split up our 4 samples
at each of the 4 sites in the laboratory.
Table 1: Site description of the location where we collected out 4 samples, in reference to figure 3.
Site number and grid
reference
Site description
Site 1 (NY 780,435) This site is located approximately 10 meters (m) downstream of the last
mining pollution discharge, allowing us to measure the anion and cation
concentration of the waterway leaving the mining site.
Site 2 (NY 783, 433) The next site is upstream of site 1, and is also upstream of another
discharge that is located between site 1 and 2, this gives us a better change
of identifying the effect of the discharges.
Site 3 (NY 787,428) Located just before River Nent splits up into a number of tributaries,
therefore we measured the water quality of the river before the tributaries
entre the river, allowing us to analyse the effect of the tributaries on the
Cations and Anions.
Site 4 (NY 789, 424) Lastly site 4 was the most upstream section of the Nent River, therefore we
would be collecting samples from an unpolluted water that’s has been
naturally filtered through the underlying geology.

8
Storage:
Samples were refrigerated at 4oC until we prepared or analysed the samples, maximum storage was up to
14 days for alkalinity and 6 months for the remaining metals.
2.2.3 – Anion analysis:
Holding time is the amount of time ions can be held in in
solution under specific preservation conditions without affecting
the accuracy of the analysis (Epa.gov, 2016)
We did the Anion analysis well within the holding time (6months) for the best chance of accurate results.
The calibration standards were made from dry salts, into a 100ml volume with specific concentrations
(mg L-1) of ion analysed (see appendix 7). We used these to calibrate the Equipment before each ion
analysis.
Four accuracy check solutions (100ml) were made, two contained 10mg L-1 of the anions and the
remaining two contained 5mg L-1. Three blank solutions were also made from deionized water to check
ensure the Equipment wasn’t reading ions when there wasn’t any for accuracy (Intox.com, 2016). Finally,
diluted sample by a factor of 5, to ensure the rods could absorb all the ions in solution, thus prevent
supersaturating.
Ion Chromatography was our definitive analysis, which uses ion-exchange ions to separate molecular ions
based on their interaction with the resins (Chemicool.com, 2016).
Equipment components (figure 5):
1. Dionex ion-chromatography system (ICS-1000)
2. AS40 autosampler, which is chemically inert and works with a variety of elements, it uses ion-
exchange resins to separate ions in aqueous solutions (Dionex, 2008).
Figure 5: Diagram of the Ion chromatography Equipment, with the solution getting pumped in and
through the ion-exchange column and then through the conductivity detector (Bryn, 2015).
Table 2 - Holding times of the Anions analysed (ALS Environmental, 2013).
Ion (anion) Holding times
Cl- 6 months
NO3- 6 months
SO43
- 6 months
PO44
3- 6 months
HCO3
- 6 months

Oliver Ben Field
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3. Column type - IonPac As14A
4. The eluent (within the column): 8.0mM Na2CO3/1.0mM NaHCO3 solution,
5. Injection loop: 25ul (microliters)
6. Flow rate: 1ml/min. Increased flow rate results in easier distinction of which ion is getting
absorbed at a given time (figure 6) (Srinivasan et al., 2010), (see appendix 13).
First we calibrated the equipment using the known standard solution, a chromatogram (a plot of the
detector output vs. time), which converts each peak area to an ion concentration and produces results in a
graph (thermo scientific, 2015). An R2 value is given to show the correlation, which ensures accurate
results, an R2 value >9.4 the Equipment was calibrated (see appendix 14).
Each analysis took between 15-25 minutes, Na was analysed first because of contamination concert from
sweat. We calibrated the Equipment before each ion analysis to ensure the Equipment’s accuracy via
blank solution testing. Then we test the ion solutions to identify the peak of each ion and the time of
absorption onto the positive exchange resins to attract negative ions (ammonium group) within the
column (Jones, 2015).
Figure 6: the effect of flow rate on the overall run time was studied for a new
IonPac AS22-Fast column at various flow rates shown above (Srinivasan et al.,
2010).

10
The retention time is the time it takes for a solute to travel through the column, whilst the surface area
represents the ion concentration (Chem.agilent.com, 2016). In figure 7 Sulphate has the highest volume
and the longest retention time of 12.13 minutes. Nitrate has the lowest concentration with an 8.02 min
retention time. Chloride has the fastest retention time (4.99 min) with a relatively small concentration,
Phosphate was non identifiable. This plot was done for every sample.
2.2.4 Cation analysis:
Cations were prepared within 10 days for Atomic
Absorption Spectroscopy (AAS) analysis, we also could
have also Colorimetry and Autoanalyser (see appendix 4).
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
-1.00
-0.50
-0.00
0.50
1.00
1.50
2.00
2.50
3.00
3.50
4.00
4.50
Edmond 19.11.15 #26 1B1 ECD_1
µS
min
1 - Chloride - 4.990
2 - Nitrate - 8.203
3 - Sulphate - 12.133
Figure 7: showing the retention times for Chloride, Nitrate
and Sulphate, with the surface area of the peak representing
for sample 1B1 the output.
Table 4 - Holding time of the Cations
analysed (ALS Environmental, 2013).
Ion (Cation) Holding time
Na+ 6 months
K+ 6 months
Ca2+ 6 months
Mg2+ 6 months
Pb2+ 6 months
Zn2+ 6 months
Table 3 – Anion (1B1) retention times (min)
Standard 1B1 retention
times (min)
Chloride (mins) 4.99
Nitrate (mins) 8.02
Sulphate (mins) 12.13
Phosphate
(mins)
N/A

Oliver Ben Field
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Two sets of calibration standards at a given concentration were made, one set for micronutrients (Zn and
Pb) and the other for macronutrients (Na, K, Ca and Mg) (see appendix 7)
Four accuracy checks were prepared; two of the four contained 2.50 mg L-1 each of Na, K, Ca and Mg
and 2000mg L-1 Cs (caesium) as an ionizing suppressant, which ensures balanced atoms through the
release of electrons (Robinson, Skelly and Frame II, 2014). The other two contained 0.50mg L-1 of Pb and
Zn with no Cs. Three blanks of deionized with 2000mg L-1 of Cs and another three without Cs were
prepared.
Finally, diluted Na, K, Ca and Mg solutions ten times with 2000mg L-1 of Cs, whilst Pb nd Zn required
no dilution. This was to ensure accurate and precise results.
AAS was carried out for our further analysis, it measures the intensity of the light absorbed when photon
move from ground state to excited state shown in figure 8.
Flame used: acetylene
The atoms are absorbed by the wavelength emitted from the hollow cathode lamp, the monochromator
isolates the wavelength chosen and photomultiplier quantifies the amount of light being absorbed by the
atom cloud shown in figure 9. The reduction of light intensity is related to the number of absorbing atoms
and this is proportional to their concentration in the sample (see appendix 1), (Jones, 2015).
Figure 8: Illustrating what the photon from the element being analysed does when it
goes from a ground state to an excited atom, thus getting absorbed.
Wavelength of each atom:
 K - 766.5 nm (Sisbl.uga.edu, 2016)
 Na – 589,590 nm - (physics rutgers, 2015)
 Ca - 422.7 nm
 Mg - 285.2 nm. (Chemistry 321L manual, 2015)

12
Appendix 11 lists positives and negatives
Figure 9: Diagram of the Atomic Absorption Spectroscopy equipment, and the
route of the sample
Table 7: physical, chemical and background absorbance interfaces compensated for
Interference
considered
Description
Physical High viscosity reduces the speed of AAS< to avoid this we:
 Diluted the solution
 Used the same solvent for samples and standards
 Calibrated by standards (Jones, 2015).
Chemical Sample must be volatilised, three chemical interferences could have affected this:
 Formation of stable oxides, resulting in reduction of ground state atoms.
Therefore increase the heat of the flame.
 Ca absorbance reduced in presence of phosphate as forms calcium pyrophosphate
that is stable in acetylene flame. To prevent this you use a hotter flame.
 Ionization, therefore added an ionizing suppressant (Cs) (Jones, 2015).
Background
absorbance
Occurs when absorbance bands coincide with atomic absorption wavelengths, it occurs at
wavelengths <300nm. So we used HCL lamps that record the total absorbance of atoms
and molecules, and we also used a D2 lamp only measures background absorbance
(molecules). The computer subtracts the D2 lamp from the HCL to give us the atomic
absorbance.

Oliver Ben Field
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2.3 - Calculations of raw data:
3.1 – Cation and Anion results
Appendix 9 for description the ions in aquatic systems
3.1.1 –Cation analysis
Lower Limit of Detection (LLD):
1. Dilution corrections - subtracted the average blank concentration from every sample (1A1 to
4B2) and multiplied it by 10 to improve accuracy.
2. Precision - calculated the average and standard deviation (Stdev) of each ion of each site. Then
divided the Stdev by the average and multiplied this result by 100 to work out the precision
(%RDS).
3. Accuracy – the accuracy check standards are subtracted from blank concentration averages, and
then averaged. Then subtracted the volume of the accuracy check (i.e. Cations = 2.5(mg/L)) off
the average accuracy check concentration and divided this by the volume of the accuracy check,
and multiply by 100.
4. LLD – average and standard deviation of the blank and add them together and multiply the Stdev
by 3. Lastly subtract the average blank concentration from the previous result and multiply it by
the dilution of the ion (i.e. Na = 10)
5. Charge balance - divide the dilution correction by the atomic mass, and multiply it by the charge
(i.e. Na+ = 1). Add up the total Cations and Anions through this equation: 100 × (total Cations –
total Anions)/ (total Cations + total Anions) for each sample.
Table 8: Cation LLD, with named samples lower than the LLD of the specific ion
Cation Na K Ca Mg Pb Zn
Lower Limit of
Detection (LLD) –
mg L-1
0.0 0.17 0.62 0.17 0.08 0.02
Samples lower
than LLD
N/a N/a N/a N/a 1B2 (-0.03)
3A2 (0.03)
3B2 (0.06)
4A1 (-0.03)
4A2 (-0.05)
4B1(0.06)
4B2 (0.03)
N/a

14
3.1.2: Sodium
Figure 10 – shows the sodium (Na) concentration in relation to the position on the
river, 1A1 – 1B2 is the first site, therefore water sample of River Nent as it leaves
the mine. 4A1 - 4B2 is the last sample of the source of river Nent, therefore no
pollution.
y = -0.3837x + 10.562
R² = 0.3921
0.00
2.00
4.00
6.00
8.00
10.00
12.00
14.00
16.00
18.00
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
Naconcentration(mg/L)
Sample number (1A1 = first sample, 4B2 = last sample).
Na concentration as we move up the
River Nent (mg/L)
Na concentration (mg/L)
Linear ( Na concentration
(mg/L))
Table 9: cation results
Sample and
site
Na (mg L-1) K (mg L-1) Ca (mg L-1) Mg (mg L-1) Pb (mg L-1) Zn (mg L-1)
1A1 16.90 5.97 89.27 23.43 0.34 3.92
1A2 13.00 5.77 85.67 23.23 0.08 3.93
1B1 8.10 4.97 82.67 22.43 0.24 3.89
1B2 6.80 3.47 82.77 22.43 0.08 3.93
2A1 4.70 1.47 32.07 6.93 0.12 1.85
2A1 6.60 3.67 36.37 7.83 0.15 1.88
2B1 4.80 1.17 31.17 7.03 0.36 1.84
2B2 2.80 0.77 33.37 6.93 0.16 1.86
3A1 7.40 1.47 17.27 4.63 0.28 0.72
3A2 6.30 1.57 24.77 4.53 0.08 0.74
3B1 4.60 19.07 18.57 5.03 0.26 0.72
3B2 7.00 1.87 19.77 5.03 0.08 0.72
4A1 4.00 1.17 12.17 2.93 0.08 0.16
4A2 3.20 1.17 7.07 2.33 0.08 0.17
4B1 5.70 0.87 18.17 4B1 - 4.33 0.08 0.15
4B2 5.70 1.17 9.67 4B2 - 2.93 0.08 0.16
2.5mg L-1
major cations
accuracy check
Accuracy =
10.20
Accuracy
= -15.93
Accuracy
= 47.47
Accuracy =
16.13
Accuracy =
51.67
Accuracy =
45.33
0.5mg L-1
major cations
accuracy check
LLD
(detection
limit)
0.00 0.17 0.62 0.17 0.08 0.02

Oliver Ben Field
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Na concentration has a higher concentration at site one (1A1 – 1B2), in comparison to site 4 (4A1 – 4B2),
(figure 10). For example sample 1A1 has a concentration of 16.90 mg L-1, whilst sample 4A2 has a
concentration of 3.20 mg L-1. The R2 value is 0.39, thus showing a weak correlation, however it still
shows that there is a minor correlation suggesting that the Na concentration is slightly higher leaving the
mine than it is entering.
3.1.3: Potassium
These results are relatively negligible, mainly because of the anomalous sample 3B1 (Fig 11), this causes
the results of site 3 being misleading and negatively affecting the R2 of the graph. The R2 value is 0.034
showing no correlation from site 1 to 4, as a value of 0 represents no relationship. However if 3B1 was
cancelled out it would show a better correlation, with the concentration being greater leaving the mine
(5.97 mg L-1) than it is entering the mine (0.87 mg L-1).
3.1.4 - Calcium
Figure 11 – Showa the potassium (K) concentration in relation to the position on the
river, 1A1 – 1B2 is the first site; therefore water sample of River Nent as it leaves the
mine. 4A1 - 4B2 is the last sample of the source of river Nent, therefore no pollution.
y = -0.1413x + 4.8864
R² = 0.0339
0.17
5.17
10.17
15.17
20.17
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
Kconcentration(mg/L)
K concentrationas we move up the
River Nent (mg/L)
K concentration (mg/L)
Linear ( K concentration
(mg/L))

16
The first visual impression (Fig 12) is that there is a strong trend from low concentrations at site 1 to
gradually increasing concentrations to site 4. The R2 value of 0.8, suggests an obvious correlation. The
results also back this up, as the Ca concentration leaving the mine is 89.27 mg L-1 (1A1), whilst the value
entering the mine is 7.07 mg L-1 (4A2) with intermediate value at site 2 at 36.37 mg L-1 (2A2).
3.1.5: Magnesium
Mg concentration clearly has a significant difference between site one and site 4. An R2 value of 0.74
signifies a clear correlation. The figures show that site 1(23.43 mg L-1) is substantially higher than site 4
Figure 13 – Shows the Magnesium (Mg) concentration in relation to the position on the
river, 1A1 – 1B2 is the first site; therefore water sample of River Nent as it leaves the mine.
4A1 - 4B2 is the last sample of the source of river Nent, therefore no pollution.
y = -1.186x + 21.362
R² = 0.7374
0.17
5.17
10.17
15.17
20.17
25.17
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
Mgconcentration(mg/L)
Mg concentration as we move up the
River Nent (mg/l)
Mg concentration (mg/l)
Linear ( Mg concentration
(mg/l))
Figure 12 – Shows the Calcium (Ca) concentration in relation to the position on the river, 1A1
– 1B2 is the first site, therefore water sample of River Nent as it leaves the mine. 4A1 - 4B2 is
the last sample of the source of river Nent, therefore no pollution.
y = -4.5013x + 82.561
R² = 0.802
0.62
20.62
40.62
60.62
80.62
100.62
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
Caconcentration(mg/L)
Ca concentrationas we move up the River
Nent (mg/L)
Ca concentration (mg/L)
Linear ( Ca concentration
(mg/L))

Oliver Ben Field
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17
(2.93 mg L-1). Therefore the Mg concentration entering the mine is considerably lower than the
concentration leaving (Fig 14).
3.1.6 – Lead (Pb)
Pb results are negligible and unreliable because of the lack of precision and accuracy, with a number of
values are less than the blank concentration named above. These concentrations of Pb are in minor
amounts because lead is a micronutrient, however there is no identifiable trend because of the huge range
of results within each site (Fig 15). Therefore the results are fairly negligible, which is reiterated by an R2
value of 0.19, suggesting no significant correlation.
Figure 15 – shows the Lead (Pb) concentration in relation to the position on the
river, 1A1 – 1B2 is the first site, therefore water sample of River Nent as it leaves
the mine. 4A1 - 4B2 is the last sample of the source of river Nent, therefore no
pollution.
y = -0.0054x + 0.2051
R² = 0.0759
0.08
0.13
0.18
0.23
0.28
0.33
0.38
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
Pbconcentration(mg/L)
Sample number (1A1 = first sample and 4B2 = last sample)
Pb concentration as we move up the
River Nent (mg/l)
Pb concentration (mg/l)
Linear ( Pb concentration
(mg/l))

18
3.1.7 – Zinc (Zn)
Zn results are very precise due to little fluctuation of results at each sample site (Fig 16). This chart also
shows a clear trend between the Zn concentrations as we move up the River Nent. An R2 value of 0.90
showing a strong correlation, this shows that the Zn concentration is higher leaving the site (3.90 mg L-1)
than the water entering the site (0.16 mg L-1). However, the high accuracy value suggests this may not be
the true reflection of the site.
3.2.1 –Anions Analysis
Some of the values came out at the same concentration or lower than the blank, therefore it was
unidentifiable 1A2 is seen to have a concentration of -1.95 mg L-1 of NO3 less than the blank
concentration.
Figure 16 – Shows the (Zn) concentration in relation to the position on the river, 1A1
– 1B2 is the first site, therefore water sample of River Nent as it leaves the mine. 4A1
- 4B2 is the last sample of the source of river Nent, therefore no pollution.
y = -0.2386x + 4.0478
R² = 0.8961
-1.00
0.00
1.00
2.00
3.00
4.00
5.00
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
Znconcentration(mg/L)
Sample number (1A1 = first sample and 4B2 = last sample
Zn cocnentrqation as we move up the
River Nent (mg/l)
Zn concentration (mg/l)
Linear ( Zn concentration
(mg/l))
Table 10 - Anions LLD and the anion samples less than LLD
Anions Cl (2) NO3 SO4 PO4 HCO3
Lower Limit of
Detection (LLD) –
mg L-1
4.6 10.13 0.00 0.00 0.00
Samples less than
LLD
2A1 (2.83)
2B1(3.05)
3B2 (2.92)
3B1 (3.64)
4A2 (3.50)
4B1 (2.77)
and
4B2 (2.89).
1A1 (-1.95)
1A2 (-1.95)
1B1 (2.01)
1B2 (1.93)
4A2 (-1.95)
4B1 (0.28)
and
4B2 (-1.95).
N/A N/A ****

Oliver Ben Field
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19
Table 11: Completed Anion results
Name Cl (mg L-1) NO3 (mg L-1) SO4 (mg L-1) PO4 (mg L-1)
HCO3
(alkalinity)
concentration
(mg L-1)
1A1 5.59 10.13 123.02 0.00 180
1A2 5.84 10.13 127.15 0.00 188
1B1 5.48 10.13 128.00 0.00 170
1B2 6.13 10.13 127.09 0.00 172
2A1 4.6 18.55 31.83 0.00 45
2A1 4.97 21.59 35.72 0.00 38
2B1 4.6 18.07 31.65 0.00 75
2B2 4.6 16.58 29.88 0.00 75
3A1 5.56 74.77 21.50 0.00 10
3A2 5.39 63.27 22.96 0.00 15
3B1 4.6 12.96 19.80 0.00 30
3B2 20.37 18.47 29.16 0.00 29
4A1 5.03 51.77 7.04 0.00 10
4A2 4.6 10.13 6.43 0.00 15
4B1 4.6 10.13 6.68 0.00 13
4B2 4.6 10.13 7.10 0.00 13
10mg/L anions
accuracy
check
Accuracy = -
27.93
Accuracy = -
15.51
Accuracy = -
7.91
Accuracy = -
17.40
10mg/L anions
accuracy
check
5mg/L anions
accuracy
check
Accuracy = -
77.63
Accuracy = -
30.38
Accuracy = -
42.67
Accuracy = -
100.00
5mg/L anions
accuracy
check
LLD = 4.60 LLD = 10.13 LLD= 0.00 LLD = 0.00

20
2.2.3 - Chloride (Cl)
An R2 value of 0.00 shows no correlation between Cl concentrations from site 1 to 4, thus suggesting that
the mining activity has no effect on the Cl concentration in the river. This is backed up through the
concentrations at 1A1 is 5.59mg L-1 and 4A1 is 5.03mg L-1 this shows that there isn’t a significant
difference in the Cl concentration in site 1 compared to site 4 (Fig 17). The anomalous result (3B2) with a
concentration of 20.37 mg L-1 skewed the results at site 3, leading to heightened insignificance.
3.2.4 - Nitrate (NO3)
Figure 17 – Shows the second Chloride (Cl) lab analysis concentration in relation to the position
on the river, 1A1 – 1B2 is the first site, therefore water sample of River Nent as it leaves the
y = 0.0634x + 5.4008
R² = 0.0094
4.60
9.60
14.60
19.60
24.60
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
Clconcentration(mg/L
Cl concentration as we move up the River
Nent (mg/L)
Cl concentration (mg/L)
Linear ( Cl concentration
(mg/L))
Figure 18 – Show the Nitrate (NO3) concentration in relation to the position on the river, 1A1
– 1B2 is the first site, therefore water sample of River Nent as it leaves the mine. 4A1 - 4B2 is
the last sample of the source of river Nent, therefore no pollution.
y = 0.7159x + 15.774
R² = 0.041
10.13
30.13
50.13
70.13
90.13
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
NO3concentration(mg/L)
Sample site (1A1 = first sample and 4B2 = last sample
NO3 concentration as we move up the
River Nent (mg/L)
NO3 concentration (mg/L)
Linear ( NO3 concentration
(mg/L))

Oliver Ben Field
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21
These results are somewhat negligible; the R2 value is 0.04, suggesting no correlation between the NO3
concentrations leaving and entering the mine. Site 3 has a large fluctuation as 3A1 has a concentration of
74.77 mg L-1 and sample 3B1 has concentration of 12.96 mg L-1, thus imprecise. Sample 4A1 is
anomalous wit ha value of 51.77-mg L-1 compared to the next highest concentration of 0.28 mg L-1 (Fig
18). However, the data shows that the NO3 concentration at site 3 and 4 are higher than 1 and 2, so if
anything the mining activity could act as an NO3 reducing agent.
3.2.5 – Sulphate (SO4)
The R2 value is 0.74 showing a relatively strong correlation between an increase in SO4 concentration as
we move down the Nent River (Fig 19). The concentration increases 3 fold from site 4 to site 3 from
around 7mg L-1 to around 21 mg L-1. The SO4 concentration increases hugely from site 3 to site 4 to a
SO4 concentration more than 120 mg L-1, suggesting a significant difference in the SO4 concentration
leaving the mine (126.32mg L-1) compared to the concentration entering the mine (6.81mg L-1).
3.2.7 – Phosphate (PO4)
Figure 20 – Shows the Phosphate (PO4) concentration in relation to the position on the
river, 1A1 – 1B2 is the first site, therefore water sample of River Nent as it leaves the
y = 0
R² = #N/A
0.00
0.50
1.00
1A1
1A2
1B1
1B2
2A1
2A1
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
PO4concentration(mg/L)
PO4 concentrationas we move up the
River Nent (mg/L)
PO4 concentration
(mg/L)
Linear (PO4
concentration (mg/L))
Figure 19- Shows the Sulphate (SO4) concentration in relation to the position on the
river, 1A1 – 1B2 is the first site, therefore water sample of River Nent as it leaves the
y = -7.0433x + 117.62
R² = 0.741
-40.00
-20.00
0.00
20.00
40.00
60.00
80.00
100.00
120.00
140.00
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
SO4concentration9mg/L)
SO4 concentration as we move up the
River Nent (mg/L)
SO4 concentration (mg/L)
Linear (SO4 concentration
(mg/L))

22
These results are negligible and the absence of concentration results in the inability to analyse PO4.
3.2.8 – Alkalinity (HCO3)
The R2 value 0.74 shows a relatively strong correlation, signifying an increase in the HCO3 concentration
from site 4 to site 1. The average concentration at site 4 is 12.75mg L-1, this concentration increases 14
fold to reach the 177.5mg L-1 concentration at sight 1, showing a significant difference between the
concentration entering the mine (site 1) in comparison to the concentration leaving the mine (site 4). In
between sites 4 and 1 there is a gradual increase from site 4 to site 3 and another slight increase from site
3 to site 2.
Figure 21 – Shows the HCO3/ alkalinity change in relation to the position on the river, 1A1 –
1B2 is the first site, therefore water sample of River Nent are as it leaves the mining site. 4A1-
4B2 is the last sample of the source of river Nent, where there has been no pollution and is
predominately groundwater.
y = -10.084x + 168.16
R² = 0.7424
-50
0
50
100
150
200
1A1
1A2
1B1
1B2
2A1
2A2
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
HCO3concentration(mg/L)
HCO3 (alkalinity) concentrationas we
move up the River Nent (mg/L)
HCO3 (alkalinity)
concentration (mg/L)
Linear (HCO3 (alkalinity)
concentration (mg/L))

Oliver Ben Field
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23
3.3 – Charge balance calculations
The charge balance is the amount of positive and negative charges in solution (Ion.chem.usu.edu, 2015).
Overall the charge balance is positive apart from sites 3A1, 3B2 and 4A1 (Fig 22), these are only minor
in compression to positive charges such as 44.86 mg L-1 at site 4B1. A value of zero means that the rivers
Figure 22: Shows the charge balance as you move up the Nent River, the furthest
downstream point are samples 1A1 – 1B2 (site 1), the furthest upstream points are
from 4A1 – 4B2 (site 4).
-100.00
-50.00
0.00
50.00
1A1
1A2
1B1
1B2
2A1
2A1
2B1
2B2
3A1
3A2
3B1
3B2
4A1
4A2
4B1
4B2
chargeBalance(meq)
Sample number (1A1 = first sample, 4B2 = last sample)
Charge balance within the water system
as we move up the River Nent.
Charge balance
Table 12: Charge balance of the Anions and Cations of the river Nent.
Total
Cations
Total
Anions
Charge
balance
7.39 5.64 11.77
7.02 5.87 7.30
6.57 5.64 6.47
6.48 5.67 5.50
2.47 1.78 16.23
2.90 1.86 21.94
2.43 2.27 3.52
2.43 2.20 5.02
1.63 1.97 -9.66
1.95 1.90 1.27
2.05 1.22 25.59
1.77 1.95 -4.82
1.06 1.29 -9.85
0.72 0.45 5.60
1.54 0.43 44.86
0.01 0.40 25.48

24
charge is in equilibrium with positive charges suggesting more Cations than Anions and negative value
have more Anions. These results seem to be fairly negligible because of the lack of precision in site 2, 3
and 4, however site 1 is relatively consistent.
3.4 – Precision:
Precision means results are in close proximity to each other, thus re-obtainable.
Na and K precision results are outside the 5% (%RDS) acceptable value, suggesting imprecise results that
are not re-attainable, as they are not in close proximity to each other. However, K 2.5mg/L accuracy
check has a value of 7.07%, thus close to 5%, suggesting fairly precise results but not at an acceptable
value.
Ca 2.5mg/L accuracy check (1.92%) and site 1 (3.66%) are precise, thus re-attainable. Site 2 is also fairly
precise (6.83%) but not acceptably so therefore not classified as re-attainable results. Site 3 (16.32%) and
site 4 (40.35%) results are imprecise, thus not re producible.
Mg site 1 (2.30%) and 2.5mg/L accuracy check (0.97%) results are precise therefore re-attainable,
however the rest of the results are outside the 5% value, thus imprecise and negligible, even though site
2’s value of 6.07% it’s not classified as precise.
Pb results are very imprecise and negligible, thus not consistent nor re-attainable. However, 0.5 mg L-1
accuracy checks have a value of 6.53%, but not of an acceptable value despite its low value.
Table 13: Cation macronutrient precision (%RDS) analysis.
Site
number
Precision
(%RDS)
Na
Precision
(%RDS)
K
Precision
(%RDS)
Ca
Precision
(%RDS)
Mg
1 41.46 22.52 3.66 2.30
2 32.85 73.51 6.83 6.07
3 19.55 145.51 16.32 5.47
4 27 13.74 40.35 27.08
2.5
mg/L
accuracy
checks
18.22 7.07 1.92 0.97
Table 14: Cation micronutrients precision (%RDS) analysis.
Site number Precision
(%RDS)
Pb
Precision
(%RDS)
Zn
1 117.35 0.48
2 54.60 0.92
3 81.29 1.39
4 878.31 5.21
0.5 mg/L accuracy
checks
6.53 21.41

Oliver Ben Field
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25
Zn, 0.5 mg L-1 accuracy checks (21.41%) are imprecise, site 4 is only 0.21% off being classed as precise
however by definition it is imprecise. Site 1 to 3 results are very precise as the highest value is 1.39%
therefore reliable and precise.
Cl and NO3 results are all out-side the acceptable value by a considerable margin, thus imprecise and un-
attainable. However, site 1 is only 0.05% outside the acceptable level, thus showing relatively precise
recordings. NO3 site 1 has a value of 21566.21%, thus entirely negligible.
SO4, site 1 (1.77%) and 4 (4.65%) are precise, thus re-attainable. However, the rest are imprecise and un-
attainable. Site 2 (7.62%) is relatively precise but not of an acceptable value.
PO4, only the accuracy checks are available with a result of 116.25%, thus imprecise and negligible.
HCO3, site 1 has an acceptable precision of 5%, thus re-attainable. However, the rest of the results are
imprecise and un-attainable.
3.5 – Accuracy:
Accuracy = results represent the true value of the solution (in our case), thus the % deviation of the
known values
Table 16 shows that Na is only 0.2% off being an acceptable accuracy (10%), however the rest of the
results are considerably above the acceptable level, thus suggesting negligible, inaccurate that don’t
represent the true value of the ions in solution.
Table 15: Anion precision (%RDS) analysis
Site number Precision
(%RDS)
Cl
Precision
(%RDS)
NO3
Precision
(%RDS)
SO4
Precision
(%RDS)
PO4
Precision
(%RDS)
HCO3
1 5.05 21566.21 1.77 N/A 5
2 29.70 11.24 7.62 N/A 34
3 89.26 73.68 17.46 N/A 48
4 29.30 220.23 4.65 N/A 16
Anion accuracy
check
85.54 48.86 61.12 116.25 N/A
Table 16: Cation accuracy analysis
Accuracy
(%) Na
Accuracy (%) K Accuracy
(%) Ca
Accuracy
(%) Mg
Accuracy
(%) Pb
Accuracy
(%) Zn
10.20 -15.93 47.47 16.13 51.67 45.33

26
All the results in table 17 are above the acceptable value (10%) apart from 1 SO4 value for 5mg/L at -
7.91%, suggesting acceptable accuracy. The rest of the results are negligible and inaccurate, thus not
representing the true ion concentration in solution e.g. PO4 10mg/L is -100.00%, and NO3 5mg/L is least
inaccurate value (-15.51%).
3.6 – other essential recordings
The results taken in the field are incomplete with about half the data missing (table 18), thus somewhat
negligible. However, you can see some trends such as a slight increase in temperature from site 4
(8.360C) to site 1 (8.89oC), also pH declines from pH 8 at site 2 to 7.73 at site 1. Clear correlations of
TDS starting at 38 mg L-1 (site 4) and increases to 368 mg L-1 (site 1), conductivity has a similar pattern
to TDS, the starting value of 57 (uS/cm) (site 4) and leads to 533 (site 1). Oxidation-reduction potential
(EH (mV)) also has a slight increase from 91 at site 1 to 137.5 at site 4. Alkalinity (mg L-1 of CaCO3)
also increases from 14.2 (site 4) to 118.3 (site 1).
Table 17: Anion accuracy analysis
Accuracy
(%) Cl (2)
Accuracy
(%) NO3
Accuracy
(%) SO4
Accuracy
(%) PO4
Accuracy
(%) HCO3
5 mg/L -32.33 -15.51 -7.91 -17.40 N/A
10mg/L -79.01 -30.38 -42.67 -100.00 N/A
Table 18: results taken in the field
Name Location
Field
Alkalinity
(mg/L as
CaCO3)
Conductivity
(uS/cm)
PH
EH
(mV)
TDS
(mg/l)
Tem
p (C)
1A1 NY780435 98 532 7.69 140 368 8.89
1A2 NY780435 133 534 7.77 135 368 8.77
1B1 NY780435 124
1B2 NY780435
2A1 NY783433 191 8.04 136 125 9.02
2A1 NY783433 191 7.99 133 126 8.64
2B1 NY783433 191 7.97 128 126 8.53
2B2 NY783433
3A1 NY787428
3A2 NY787428
3B1 NY787428
3B2 NY787428
4A1 NY789424 21 57 7.82 91 38 8.36
4A2 NY789424 13
4B1 NY789424 12
4B2 NY789424 12
13

Oliver Ben Field
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27
3.5 – piper diagram
In the piper diagram (figure 23) sample 1 and 2 have a higher amount of Mg and Ca, whilst site 3 and 4
have high concentration of Mg and Ca with a substantial amount of Na and K (Survey, 2016).
4.1 Discussion
4.1 Overview:
Warmer temperatures, higher oxygen availability and more acidic conditions promote the dissociation of
ions. Oxygen react with ions to create energy, leading to increased kinetic energy, thus increasing the
chance of particles colliding leading to chemical reactions (WhatReactions, 2016), the same occurs with
increasing temperature. Acidic increases the dissociation of ions to maintain equilibrium, e.g. CaF2 as F-
ions reduce to form HF (White, 2016):
Figure 23: Piper diagram showing the relative ionic composition of the water samples. The
concentrations are expressed as % meq L-1.

28
The complexity of the ions is an important factor, as the more complex chemical structure such as micro
nutrients are less reactive, hence there low abundance dissolved. Macronutrients are in higher abundance
due to less complex chemical structures, thus easily dissolved (WhatReactions, 2016).
4.2. Macronutrients:
These are essential for growth, metabolism, and other body functions and are needed in large quantities
(‘macro’ means large), (Sciencelearn Hub, 2016).
Cations:
Sodium and Potassium:
The correlation for Na is strong because they are easily dissolved ions therefore the toxic minerals don’t
have a great affect on their content throughout the River Nent. They get constantly absorbed by aquatic
flora and fauna and dissolve when water runs through the geology and soil, which maintains equilibrium
(Sciencelearn Hub, 2016). K would be similar if sample 3B1 was so anomalous, the assumption that this
is human error as the rest of the results are fairly consistent.
Magnesium and Calcium:
Ca and Mg ion dissolved from most soils and rocks, especially limestone, which is more prominent in the
lower catchment (figure 2), the mining intensifies the limestones exposure, thus promoting disassociation
of ions. Hence the sudden Ca and Mg increase at site 3 and 4 (Ngwa.org, 2016). Americas average Ca
concentration is 21.8mg L-1, even in different continents the concentration are similar to site 2 (table 9),
(Morr et al., 2006).
Anions:
Chloride and Nitrate:
Cl blanks were of poor quality, resulting in results being below the lower limit of detection, with only one
result being substantially above the LLD.
Decaying OM, sewage and nitrate fertilizers produces nitrate, these were minimal in the Nent catchment,
causing low nitrate concentration. However, there were a few large concentrations at site 3, which could
be caused by nitrate-contaminated tributaries that feed the river Nent (Ngwa.org, 2016).
Phosphate:
Results were non-existent because phosphate is often the limiting factor for growth of flora, therefore
only containing minor amounts and the lack of Phosphorous fertilizers in the catchment. Therefore there
is no PO4 source, also the IC my have struggled to absorb the ion (Bryn, 2016).
Sulphate:
Sphalerite (ZnS) in the spoil heaps allows the S to become dissociated when weathered S gets oxidized to
form SO4 (Sulphate) (Lenntech, 2015). The reason why there is more sulphate at site 1 than 2, 3 and 4 is
because of the mine discharge 10 m upstream of site 1.
Alkalinity (HCO3)
Increased HCO3 at site 1 and 2 compared to site 4 is because of the dissociation of CO3 from CaCO3 in
limestone, which reacts with free H+ ions. This occurs further downstream because of the increased
exposure and abundance of limestone.

Oliver Ben Field
130074056
29
4.3 - Micronutrients:
They are essential to the human health in minor amounts, however if we have too much of these minerals
then it can result in diseases such as lead poisoning (Mayoclinic.org, 2016).
Cations
Lead and Zinc:
Pb results are negligible because the concentration is very small because Pb is fairly insoluble and AAS
struggles to identify lead ions, hence Pb imprecise and inaccurate results (Bryn, 2016).
Zn has precise results because the AAS Equipment is very sensitive to Zn concentration, therefore able to
detect minor concentrations accurately and precisely. Zn is moderately mobile and dissolves from
Sphalerite therefore having higher concentrations at site Compared to site 4. The higher concentration
means the AAS picks the ions up easier (Bryn, 2016).
4.4 - Charge balance:
The total charge of this should be zero (Ion.chem.usu.edu, 2015), however our recordings are positive.
These results are because of the misuse of equipment for Cations, resulting in inaccurate results (Nuttall
and Younger, 2015). This is because when we measured the conductivity and ÷ 100 to give the total
Cation and Anions in the field, it gave us poor charge balance when expressed as meq L-1. Resulting in
the Cation concentration being too high (Nuttall and Younger, 2015).
4.5 -Accuracy and precision
Both Anion and Cation results had varied accuracy and precision because of differential contamination
between samples for precision and for varied accuracy because some accuracy check solutions were made
well, but others were made poorly.
4.6 - In field results:
Alkalinity is linked to the underlying geology and the high abundance of limestone, containing CaCO3
that acts as a buffer to the acidity. The pH decrease slightly at site 1 because of the increasing number of
dissolved toxic ions, but the pH is still relatively high despite the toxicity of the ions.
Higher concentration of TDS at location, which in turn increase the conductivity of the water system at
site 1 but is less at site 4 because of the reduced TDS. These tend to come from the clay bound geology
(Till) (Environmental Measurement Systems, 2016). TDS has lead to the increase in EH, which has
developed reducing conditions (Wiley.com, 2016).
5 - Conclusion
There are more dissolved ions further down stream compared to the concentration at the source of the
river because of increased exposure of rock because of the mining activity, as well as various discharges
from the mine. The analytic techniques were not as accurate or precise as we hoped because of the
inaccurate accuracy check standards and possible contamination of samples (especially Na). However
some concentrations saw good correlation as well as accuracy and precision, whilst others had negligible
concentrations, precision and accuracy because insolubility of the ion and the inability for the analytic
Equipment to identify the ions (PO4 and Pb). AAs and IC were quick, efficient machines that were easy
to use despite their sophistication and for the most part produced significant trends and results. However,
there were many results there were many insignificant and negligible results because of poor sample
preparation for analysis.
6 - Limitations
 Could of used nitric oxide flame to improve Ca and Mg precision and accuracy.

30
 Increase the number of samples
 Make sure we record all data collected in the field
 Seasonal and diurnal variety throughout the year, therefore do repeats in different seasons and
times of day.
 Use better Equipment to analyse minor concentrations such as lead, which are also able to identify
the ion accurately and precisely.
 Buy in accuracy check standards rather than making them, they are accurate measurements that
would improve our results.
7 - Acknowledgements
The author extends his appreciation to Bryn Jones and Martin Cooke for providing the appropriate
Equipment and also organising the required transportation to the site, this allowed us to undertake our
investigation safely, accurately and within the allotted time. Further appreciation goes out to my course
members for their fieldwork cooperation, organisation and assistance throughout the study, which
allowed us to collect the relevant sample. Also further gratitude goes out to Bryn Jones and Kath
Rothwell for overseeing and helping with laboratory work and analysis.
8 - References
 ALS Environmental, (2013) ALS RECOMMENDED HOLDING TIMES AND PRESERVATIONS
FOR WATER. Available at:
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34
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January 2016).

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9 – Appendices
Appendix 1: Background information of the ore formation
Folding and faulting
Faults formed in the late carboniferous after the batholith, with a representation of its formation in figure
5 (Bulman, 2004). Earth movements bed rock to become gently folded and fractured forming the
‘Teesdale Dome’, developing wedge shape fractures. This caused lateral and vertical slippage forming
faults that were later invaded by hydrothermal fluids, eventually depositing concentric layers of minerals.
Figure 4 show that faults occurring in hard limestone and sandstone beds create clear, open fracture with
a steep angled fault line (Bulman, 2004). Fault zones act as channels, concentrating migrating fluids in a
prominent location, producing economic mineral deposits resulting from, mineral rich hydrothermal
fluids and igneous intrusions (Holdsworth, 2001).
Formation of North Pennine mineral veins
Mineral deposits origin
Two formation types of mineralization occur at Nenthead: (1) Steeply dipping fracture-filling veins of
hydrothermal origin. (2) Mineral flats. Doming during the Paleozoic created a dense network of fractures
through the Alston Block, resulting in mineralizing hydrothermal fluids flowing into the fractures from
the buried Weardale granite. Vertical mineralization occurs with greater abundance and concentration in
more competent stratigraphic units (limestone’s and sandstones) because they create wide, open voids. In
less competent rocks (shale’s), the ore bearing veins break up, creating gouge and dragged fragments of
wall rock as well as breccia, forming small, low lying faults with poorly mineralized columns, shown in
Figure 4 (Bulman, 2004). There are also mineral flats that occur in nine different limestone’s, however
predominately occurring within the Great Limestone that occurs within the Alston Block. The flats are
split into levels of Low, Medium and High flat horizons with the Great Limestone. High flats are the best
developed because the metasomatic replacement of limestone by hydrothermal fluids, forming cavities
that produce well-formed mineral specimens in Nenthead (The Rogerley mine, 2015).
Figure 19: vein profilethrough strata ofalternatinghardness (Bulman, 2004).

36
Mineralisation occurred
260-260MA (Permian),
discovered by professor
Cann at University of
Leeds. Thus coinciding
with the underlying
granite. Figure 5 shows as
fluids move away from the
heat source (granite), there
is a decrease in
temperature that leads to
various minerals coming
out of solution depending
on their chemistry and
melting point, resulting in
deposition on the walls of
the fractures in concentric
layers. 2 gangue mineral
zones occur, known as the
inner layer that hosts
Fluorite Zone and the
outer occupies Sulphide (Bulman, 2004).
Changing temperature and chemistry of mineralising fluids resulted in different minerals getting
precipitated out at different locations in the veins forming concentric layers parallel to the wall rock,
growing out into the voids. The temperature ranged from 200oC (closest to intrusion) to 60oC (furthest
away). Early solutions were silica rich, thus depositing Quartz that hardened softer walls of which they
were deposited on. Making the wall more docile to later vein solutions. Wide scale alternation of host
rocks occurred in the early stage by iron and magnesium rich solutions, known as metasomatism, local
hardening of rocks and partial re-crystallisation (Bulman, 2004). The mineral deposits bear a close
relationship in terms of concentration and spatial variation with the focus of strain and faults with the
greatest enlargement (Clarke, 2007). Primary minerals forming at higher temperatures are pyrite, quartz,
pyrrhotite and chalcopyrite (copper sulphide); they are restricted to the copper subzone. The following
phase started with Fluorite, then quartz, followed by and finally sphalerite. Baryte and witherite were
deposited at lower temperatures therefore the last of the primary minerals to precipitate. Silver is
associated with lead because the two elements have a similar atomic radius so they are both able to
coexist in galena (on average 7 ounces of silver per ton of lead in Nent Valley).
Interesting feature of fluorite is its colour variety. The mineral creates shades of green, purple, amber and
almost colourless with the same gross chemical composition. This proves a gradual change in chemistry
and temperature during mineralisation (Bulman, 2004).
Secondary mineralisation
During secondary mineralisation the veins came in contact with slightly acidic ground water, rich in
oxygen and carbon dioxide. When it came in contact with less stable minerals they were oxidised and
secondary minerals formed. Oxidation produced metal oxides, hydroxides, sulphates and secondary
carbonates from the primary sulphide and carbonate minerals. Limonite (hydrated iron oxide) was a key
economical secondary mineral, developed from the breakdown of calcium iron magnesium carbonates,
ankerite and siderite. Occurs with Ankerite and siderite rich flats exposed to the surface and iron
Figure 20: The Weardale granite intrusion that formed the mineral veins via
hydrothermal processes and circulation (North Pennines - AONB 2015)

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carbonates are dissolved, leaving a rock rich in iron. Hemimorphite, hydrozincite and smithsonite are all
secondary minerals, derived from sulphide and sphalerite (Bulman, 2004).
Alteration of Galena produces the lead carbonate, cerussite and anglesite (sulphate). Cerussite was found
in abundance at Hughill Burn Mine in 1814 were a lead-bearing vein in the Great limestone had been
altered. It was a very soft mineral that was easily extractable; no blasting was required and resulted in a
rapid extraction (Bulman, 2004).

38
Appendix 2: affect of Pb on environmental and health risk
Environmental and Health Risks by Lead: Exposure of Pb can cause many effects depending on level and
duration of Pb. The developing foetus and infant are more sensitive than the adult. Mostly, the bulk of Pb
is received from food; however, other sources may be more important like water in areas with Pb piping
and plumb solvent water, air near point of source emissions, soil, dust and paint flakes in old houses or
contaminated land. In air, the Pb levels are brought in food through deposition of dust and rain containing
metal on crops and soil. Eight broad categories of Pb use are: batteries; petrol additives; rolled and
extruded products; alloys; pigments and compounds; cable sheathing; shot; and ammunition. In
environment, the Pb comes from both natural and anthropogenic sources. The Pb exposure can be through
drinking water, food, air, soil and dust from old paint. The Pb is among the most recycled non-ferrous
metals, so its secondary production has grown steadily. The high levels of Pb may result in toxic effects
in humans, which in turn cause problems in the synthesis of haemoglobin (Hb), effects on kidneys,
gastrointestinal tract (GIT), joints and reproductive system, and acute or chronic damage to nervous
system (Govind and Madhuri, 2014)

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Appendix 3: Heavy metal toxicity and effect on fish
Fish diversity of any regime has great significance in assessment of that zone reference to environment
and pollution, as well as it contributes to the necessary information for fisheries. Many fishes may be the
bioindicators of environmental pollutants also15-16. Now, there is a great need to adopt rational methods
and new technology in the fishing towards the conservation of fish diversity of several rivers. The
management measures aimed at conserving freshwater fishes should be part of fishery policies. The
broodstock maintenance centres and hatcheries should be established exclusively for endangered and
critically endangered indigenous fishes for their in situ conservation16-17. However, in the conservation
of fish diversity, it is essential to protect the fish from the environmental pollutants heavy metals, as these
pollutants most often contaminate the fish. Various investigators in this regard have performed several
studies. The heavy metals, e.g., As, Cd, Cu, Cr, Fe, Pb, Mn, Hg, Ni, Zn, tin (Sn), etc. are very important
pollutants which cause severe toxicity to fishes. The studies performed in various fishes showed that
heavy metals may alter the physiological and biochemical functions both in tissues and in blood Carpio.
The As and inorganic As compounds, Cd compounds, Ni compounds, crystalline forms of silica,
beryllium and its compounds have been said to be chemical carcinogens, resulting into the development
of cancer in fishes. In a study on the spotted snakehead fish (Channa punctatus, Bloch), it was observed
that when the high concentration (2 mM) of sodium arsenite (NaAsO) affected these fishes, they died
within 2.5 hr. The chromosomal DNA of liver cells were fragmented which indicated that NaAsO might
have caused death of those cells through apoptosis. The polluted marine organisms used as sea foods have
caused health hazards, including neurological and reproductive disorders in both humans and animals.
The chemicals of industrial effluents and products of ships and boats, such as heavy metals can cause
toxicity in aquatic animals (Govind and Madhuri, 2014)

40
Appendix 4: Colorometry and Autoanalyser further description
Colorimetry – this is a reagent that is added, which forms a coloured complex with the anion to be
quantified. The absorption of the coloured complex with the anion to be quantified. The absorption of the
coloured complex is measured with a UV-Ais spectrophotometer. LOOK UP – further information on
these techniques
Auto-analyser – Often based on the same chemistry as previous manual techniques (e.g. colorimetric)
auto-analysers make all necessary reagent additions and measurements automatically. LOOK UP –
further information on these techniques

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Appendix 5: holding times
Table 27: holding times of minerals
(ALS Environmental, 2013).

42
Appendix 6: A graph of our results with volume of acid on the x axis against the pH on the y
axis
Figure : Alkalinity graph through acidic titration

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Appendix 7: calibration standards for Anions
Table 21: calibration standards
Standard 1 Standard 2 Standard 3 Standard 4
Chloride (mg/L) 6.25 12.5 25.0 50.0
Nitrate (mg/L) 3.13 6.25 12.5 25.0
Sulphate (mg/L) 6.25 12.5 25.0 50.0
Phosphate (mg/L) 3.13 6.25 12.5 25.0
Table 5: calibration standard concentrations (mg L-1) for K, Na, Ca and Mg
Standard 1 Standard 2 Standard 3 Standard 4 Standard 5
K 0.50 1.25 2.50 5.00 25.0
Na 1.00 2.50 5.00 10.00 50.0
Ca 5.00 12.50 25.00 50.00 250.0
Mg 2.00 5.00 10.00 20.00 100.0
Table 6: calibration standard concentrations (mg L-1) for Pb and Zn
Standard 1 Standard 2 Standard 3 Standard 4 Standard 5
Pb 0.13 0.25 0.50 1.00 5.00
Zn 0.13 0.25 0.50 1.00 5.00

44
Appendix 8: calculations
Calculations of raw data:
 Dilution corrections – subtracted the average blank concentration from the original values and
multiplied it by 10.
 Precision - we worked out the average and standard deviation of each site. Lastly we divided the
standard deviation by the average and multiplied this by 100 to work out the precision (%RDS).
Precision means the results are re-obtainable when you go out into the field and re-collected data.
 Accuracy – accuracy check standards subtracted from blank concentration averages, and averaged
them. Finally subtracted the volume of the accuracy check (i.e. Cations = 2.5) off the average
accuracy check concentration and divided this by the volume of the accuracy check, and multiply
by 100.
 LLD Detection limit calculation - standard deviation of the blank, then add the blanks average to
the standard deviation and multiply the Stdev by 3. Lastly subtract this from the average blank
concentration, and multiply this by the factor of dilution (i.e. Na = 10)
 Charge balance - meq/L = divide the dilution correction by the atomic mass, and multiply it by
the charge (i.e. Na+ = 1). Add up the total Cations and Anions, The equation: 100 × (total Cations
– total Anions)/ (total Cations + total Anions) for each sample.

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Appendix 9: Description on Anions and Cations in waterways
Cations:
Sodium (Na) is weathered out from rocks and soil then transported to the aquatic systems. However,
concentrations vary and tend to be much lower, depending on their geological conditions and wastewater
contamination. Rivers contain approximately 9 ppm of Na, in a soluble form sodium always occurs as
Na+. Sodium is present in the human body in amounts of about 100g,. However, an overdone can result in
cardiac problems. (Lenntech.com, 2015)
Rivers generally contain 2-3 ppm of K, potassium in solution is mainly present K+ ions. K is dissolved
via weathering processes in minerals such as feldspars, but is insignificant; chlorine minerals such as
carnalite and sylvite are more favourable for K production. K plays an important role in bacteria, nervous
systems and plant growth. K has a relatively high solubility therefore spreads quickly, and is seen to be a
macronutrient/essential nutrient (non-toxic) (Lenntech.com, 2015).
Calcium naturally occurs in water due to its high abundance within the earths crust. Rivers generally
have a concentration of 1-2 ppm, however in lime rich areas (i.e. limestone) the concentration can be as
high as 100 ppm. Calcium carbonate has a solubility of 14 mg/L, which is multiplied by a factor of 5 with
the presence of carbon dioxide. Calcium carbonate is the building stone for skeletons of marine
organisms, and eye lenses. The calcium storage in plants is about 1% of dry matter. Ca causes water to be
less toxic, affecting compounds such as copper, lead and zinc. Ca creates hard water, thus protects fishes
from direct metal uptake as Ca competes for binding spots in the gills. (Lenntech.com, 2015)
Commonly a concentration of Mg in rivers is around 4 ppm. Mentioned above Mg is responsible for hard
water, along with other alkali earth metals. Water with a high amount of alkali earth metals result in hard
water, and water that lacks these ions result in soft water. Mg is more soluble with increased oxygen, and
is often present as Mg2+ (aq) in water, but also as MgOH+ (aq) and Mg(OH)2 (aq). Magnesium hydroxide
solubility is 12 mg/L, whilst magnesium carbonate is more soluble than this. Minerals such as dolomite
and magnesite have high concentration of Mg, causing magnesium to be present in water as well as many
anthropogenic affects such as chemical industries adding Mg to plastics. Mg is key for any organism but
insect, it’s a central atom for the chlorophyll molecule, and is therefore essential for photosynthesis.
(Lenntech.com, 2015)
Lead is a Non-essential element, organisms don’t need lead in large quantities, but can tolerate into
certain level, if this threshold is exceeds then we start to suffer from various diseases, such as skin
pigmentation and paralysis, it also reduces our mental capacity, because lead is poisonous to bodies.
About 10-20 % of lead is absorbed by the intestines, women are generally more susceptible to lead
poisoning than men. This causes menstrual disorder, infertility and spontaneous abortion. The foetuses
are more susceptible to lead poisoning than mothers and they generally protect the mother from lead
poisoning. Children absorb more lead per unit body weight than adults (up to 40%), it can cause a lower
IQ, behavioural changes and concentration disorder. Because it’s a macronutrient river contain between 2
and 300 ppb, and the World Health Organisation (WHO) stated a legal limit of 50 ppb for lead in 1995,
which has decreased to 10 ppb in 2010. Lead is fairly insoluble and doesn’t dissolve in water under 20 oC
and pressure (1 bar). However, lead (II) acetate is a soluble compound. Led often binds to sulphur in
sulphide form, or to phosphor to phosphate form. These form of lead are incredibly insoluble and present
as immobile compounds in the environment. Lead is often soluble in soft, slightly acidic water (Kelly, Pano
and Hackley, 2016).

46
In Rome lead was often released as a by-product of silver mining, the mining that occurs at Nenthead
could have a substantial affect on the Pb concentration. Lead and its compounds are generally toxic
pollutants, it limits plants photosynthesis, but plants can still take up high amounts of lead (500 ppm)
(Lenntech.com, 2015)
Lead in petrol not just the element that counts it’s the form i.e. tetraethyl lead is worst for humans. Most
in Nenthead is inorganic, so it’s not as bad as other forms such as the forms put in petrol.
– caren Hudson Edwards – Mark mcmin
Lead is a trace metal, however is essential to flora and fauna in minor amounts, therefore it is a
micronutrient
Zinc - Rivers contain between 5 and 10 ppb of zinc, the WHO stated a legal limit of 5 mg Zn2+/L. The
solubility of Zn depends on the temperature and pH of the water. When pH is fairly neutral Zn is
insoluble. Solubility increases with increased acidity. Above pH 11 the solubility also increases. Zinc
dissolves in water as ZnOH+ (aq) or Zn2+ (aq). Zinc is present in water because of ores such as sphalerite
and smithsonite. These compounds end up in water on locations where zinc ores are found. Industrial
wastewaters also contain Zn from galvanic industries, battery production etc. Zinc is a dietary mineral for
humans and animals, but phytotoxicity may be underestimated. Zinc is a trace element and plays a key
role in enzymatic processes and DNA replication. Also the human hormone insulin contains zinc, and is
important for sexual development. A minimum amount is 2-3g as this reduces deficiencies, if this isn’t
obtained it can cause immune and enzyme systems to suffer. A zinc overdose however can cause nausea,
vomiting, dizziness, colics, fevers and diarrhoea, these occur after a 4-8g intake. (Lenntech.com, 2015)
Anions:
Cl is a major inorganic anion in freshwater, it often originates from the dissociation of salts such as
sodium chloride or calcium chloride. These and other chloride ions originate from natural minerals,
saltwater intrusion into estuaries and industrial pollution. Anthropogenic factors can have a great
influence on the Cl concentration such as salt on roads. 250 mg/L of chloride is seen to be a detectable
salty taste. The recommended maximum level of (Ruf.rice.edu, 2015)
Chloride behaves as a conservative ion in most aqueous environments, meaning its movement is not
retarded by the interaction of water with soils, sediments, and rocks. As such, it can be used as an
indicator of other types of contamination. Anomalously high concentrations can act as an “advance
warning” of the presence of other more toxic contaminants. Concentrations of Cl- in natural waters can
range from less than 1 milligram per liter (mg/L) in rainfall and some freshwater aquifers to greater than
100,000 mg/L for very old groundwaters within deep intracratonic basins (Graf et al., 1966; Psenner,
1989).
Chloride is non-toxic to humans, although there is a secondary drinking water standard of 250 mg/L. It is,
however, deleterious to some plants and aquatic biota. Chloride is also a very corrosive agent, and
elevated levels pose a threat to infrastructure, such as road beds, bridges, and industrial pipes.
(Kelly, Pano and Hackley, 2016)
Nitrogen is one of the most abundant elements. About 80 percent of the air we breath is nitrogen. It is
found in the cells of all living things and is a major component of proteins. Inorganic nitrogen may exist
in the free state as a gas N2, or as nitrate NO3-, nitrite NO2-, or ammonia NH3+. Organic nitrogen is
found in proteins and is continually recycled by plants and animals. (State.ky.us, 2015)
Nitrates in excess can cause eutrophication in downstream coastal waters by stimulating excessive growth
of algae and other aquatic plants (when nitrogen is the limiting factor for growth) and indirectly causing
oxygen deficiency in the bottom waters and reduced biodiversity. High concentration of nitrates also

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47
represents a health risk in drinking water (the World Health Organization guideline for drinking water is
less 10 mg NO3-N/L, which is the equivalent to approximately 50 mg NO3/L) (Eea.europa.eu, 2015)
Nitrites can produce a serious condition in fish called "brown blood disease." Nitrites also
react directly with hemoglobin in human blood and other warm-blooded animals to produce
methemoglobin. Methemoglobin destroys the ability of red blood cells to transport oxygen.
This condition is especially serious in babies under three months of age. It causes a condition
known as methemoglobinemia or "blue baby" disease. Water with nitrite levels exceeding 1.0
mg/l should not be used for feeding babies. Nitrite/nitrogen levels below 90 mg/l and nitrate
levels below 0.5 mg/l seem to have no effect on warm water fish. (State.ky.us, 2015)
Sulfates occur naturally in numerous minerals, including barite, epsomite and gypsum (Greenwood &
Earnshaw, 1984). These dissolved minerals contribute to the mineral content of many drinking waters.
Reported taste threshold concentrations in drinking water are 250–500 mg/litre (median 350 mg/litre) for
sodium sulfate, 250–1000 mg/litre (median 525 mg/litre) for calcium sulfate and 400–600 mg/litre
(median 525 mg/litre) for magnesium sulphate (NAS, 1977). Concentrations of sulfates at which 50% of
panel members considered the water to have an “offensive taste” were approximately 1000 and 850
mg/litre for calcium and magnesium sulfate, respectively
(Zoeteman, 1980) – in a survey of 10 -20 people.
Sulfates and sulfuric acid products are used in the production of fertilizers, chemicals, dyes, glass, paper,
soaps, textiles, fungicides, insecticides, astringents and emetics. They are also used in the mining, wood
pulp, metal and plating industries, in sewage treatment and in leather processing (Greenwood &
Earnshaw, 1984). Aluminium sulfate (alum) is used as a sedimentation agent in the treatment of drinking
water. Copper sulfate has been used for the control of algae in raw and public water supplies (McGuire et
al., 1984).
Sulfates are discharged into water from mines and smelters and from kraft pulp and paper mills, textile
mills and tanneries. Sodium, potassium and magnesium sulfates are all highly soluble in water, whereas
calcium and barium sulfates and many heavy metal sulfates are less soluble. Atmospheric sulfur dioxide,
formed by the combustion of fossil fuels and in metallurgical roasting processes, may contribute to the
sulphate content of surface waters. Sulfur trioxide, produced by the photolytic or catalytic oxidation of
sulfur dioxide, combines with water vapour to form dilute sulfuric acid, which falls as “acid rain” (Delisle
& Schmidt, 1977). (World Health Organisation, 2004)
Phosphate rock in commercially available form is called apatite and the phosphate is also present in
fossilized bone or bird droppings called guano. Apatite is a family of phosphates containing calcium,
iron, chlorine, and several other elements in varying quantities.
Phosphorus is one of the key elements necessary for the growth of plants and animals and in lake
ecosystems it tends to be the growth-limiting nutrient and is a backbone of the Kreb's Cycle and
DNA. The presence of phosphorus is often scarce in the well-oxygenated lake waters and importantly,
the low levels of phosphorus limit the production of freshwater systems (Ricklefs, 1993)
Phosphates are not toxic to people or animals unless they are present in very high levels. Digestive
problems could occur from extremely high levels of phosphate.
Phosphate will stimulate the growth of plankton and aquatic plants which provide food for larger
organisms, including zooplankton, fish, humans, and other mammals. Plankton represents the base of

48
the food chain. Initially, this increased productivity will cause an increase in the fish population and
overall biological diversity of the system. But as the phosphate loading continues and there is a build-up
of phosphate in the lake or surface water ecosystem, the aging process of lake or surface water ecosystem
will be accelerated. The overproduction of lake or water body can lead to an imbalance in the nutrient
and material cycling process (Ricklefs, 1993). Eutrophication (from the Greek - meaning "well
nourished") is enhanced production of primary producers resulting in reduced stability of the
ecosystem. In situations where eutrophication occurs, the natural cycles become overwhelmed by an
excess of one or more of the following: nutrients such as nitrate, phosphate, or organic waste. (Mr. Brian
Oram, 2015)
Alkalinity (HCO3) is the measure of the buffering capacity of river water, with a high alkalinity results
in a greater ability to neutralise acidic pollution from rainwater or wastewater. Water with a lower pH has
a lesser ability to do this. Alkalinity doesn’t just only help regulate the pH of a water body but also the
metal content. Bicarbonate and carbonate ions in water can remove toxic metals, such as lead, cadmium,
by precipitating the metals out of solution.
Alkalinity is mostly derived from the dissolution of carbonate minerals and from CO2 present in the
atmosphere and in soil above the water table. HCO3 is dominate within the neutral range (pH 5-9), CO3
2-
is above pH 9 and H2CO3 is below pH 5.
Bicarbonate values in rivers range from <5 to 730 mg/L, with a median value of 126.4 mg/L.

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Appendix 10: Planks equation (AAS)
The difference between the two orbits produces a wavelength that is emitted, worked out through Plancks
equation (E=hc/)
 E = energy difference between orbits
 H = Plancks constant
 C = the speed of light
  = Wavelength of photon (given out or absorbed)
Each of the elements have a unique wavelength, these fall within the UV-visible spectrum (160-800 nm).

50
Appendix 11: AAS advantages and disadvantages
The advantages of using this technique:
 Simple
 Low capital cost
 Low running cost
 Few spectral interfaces
Disadvantages:
 Limited working range
 Matrix interfaces
 Single element analytical capability
 Unattended operation difficult

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51
Appendix 12 – Reasons why used specific settings for Ion chromatography
Column type used was an IonPac As14A, this Analytic column was used because they have:
 High efficiency with fast analysis (8 minutes)
 Improved peak shape, efficiency, and pH stability
 Meets or exceeds performance requirements by US EPA Method 300.0 (A)
 Simplified operation with AS14A Eluent Concentrate and Combined Seven Anion Standard
The column packings for ion chromatography consist of ion-exchange resin bonded to inert polymeric
particles (typically 10 m),
Injection loop: the sample is injected into the loop, when filled it switches back into the flow path. The
sample is then injected directly into a mass spectrometer as part of a flow injection analysis (Ionsource.com,
2015).
Eluent - allowing the automatic production of high purity ion chromatography eluents, through precise
control of the electric current applied to the electrolysis of water to generate hydroxide and hydronium
ions. Eluent eliminates the need to manually prepare eluents from concentrated acids and bases, except
deionized water (Verma, 2013).

52
Figure 22: The formation of cyclothem sequences (from bottom to top). These reflect
changing sea levels and the building up of river deltas. The column on the right shows
the resulting rock sequence of limestone, shale, sandstone, coal & limestone (North
Pennines - AONB 2015).
Appendix 12 – Limestone formation - Nenthead
Cyclothem formations
In the Ordovician Period (510 and 408 million years ago (ma)) the Granite Batholith intruded the Alston
Block. Fluctuation in sea level resulted in ‘Yoredale Cycles’ to arise in the Carboniferous shown in
Figure 2 and 3 (North Pennines, AONB and European Geopark, 2010).
The Yordale Cycle:
Rock characteristics within the Yordale cycle:
Figure 3 shows the rock types within the
Yordale Cycle and attributes associated
with the formation, such as water depth,
thickness and common features found
within the beds, such as common fossils in
the limestones and marine shales, as well as
coal fragments in the sandstones.
The Great Limestone varies in thickness
frequently and to a dramatic scale. Varying
from thirty-five feet in Northumberland to
over eighty feet in Weardale. The local
variation in limestone thickness occurs due
to the development of limestone bands
within overlying shales (Johnson, 1962).
Bigger beds are better because limestones
and sandstone are harder, therefore forming
large open faults resulting increasingly
economic mineral deposits, shown in
Figure 4.
2
3
4
5
1
2
3
4
5
1
Figure 23: Cyclothem of the “Yordale Cycles”, the left hand side of
the diagram shows the variable hardness’s and the degree of
weathering that would be seen in a natural outcrop (Bulman, 2004)

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Appendix 14: calibration curves
y = 0.1666x - 0.3587
R² = 0.9721
-2
0
2
4
6
8
10
0 10 20 30 40 50 60
Area(µS*min)
Concentration standards for Chloride (mg/L)
Calibration curvefor Chloride
y = 0.0635x + 0.0087
R² = 0.9969
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
0 5 10 15 20 25 30
Area(µS*min)
Concentration standards for NItrate (mg/L)
Calibration curvefor Nitrate
y = 0.0457x + 0.0726
R² = 0.9745
0
0.5
1
1.5
0 5 10 15 20 25 30
Area(µS*min)
Concentration standards for Phosphate (mg/L)
Calibration curvefor Phosphate y = 0.0823x + 0.0041
R² = 0.9961
0
1
2
3
4
5
0 10 20 30 40 50 60
Area(µS*min)
Concentration standards for Sulphate(mg/L)
Calibration curvefor Sulphate

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