1.

Methodology
2.1. Field Methodology
The study area was divided into three sections, upstream, midstream and downstream. Sampling
was conducted on 3rd February 2017, collecting 3 triplicate water samples in each section (figure 3).
All samples were collected 5cm from the surface and stored using plastic bottles filled with no air
bubbles. Whilst all efforts were made to eliminate bias in the sample location, there were
accessibility restrictions, which made it unsafe to access the main flow of the river. GPS was used on
site to record the locations of the samples to ±3m accuracy, with field measurements for pH,
electrical conductivity (EC), dissolved oxygen (DO) and temperature taken for water parameters.

Figure 1: Map showing the sample locations.

2.2. Laboratory Methodology

Each sample was prepared for copper analysis, by filtration using No. 1 Whatman 541 filter paper,
before adding a few drops of nitric acid, for the prevention of metal absorption on the plastic bottle
and microbial growth. Inductively coupled plasma atomic absorption spectroscopy (ICP-AAS) was
used to specifically analyse copper, at the University of Derby. In the lab pH was tested again to
measure the accuracy of the field results, using a standard calibration of pH 4 and pH 7.

2.3. Quality Assurance

For quality control, a trip blank and a field blank, using deionised water samples were transported to
the sampling site. A water sample taken at Markeaton Brook was used as the control site and
analysed along with a laboratory blank (deionised water) and the other water samples.

2.4. Statistical Analysis

Pearson’s correlation was used to determine the linear association of copper concentration with the
water parameters. A two sample t-test was carried out to assess the differences between copper
concentrations in the upstream samples to the midstream and downstream samples, at a 5%
significance level.
 3. Results
The copper concentrations and water parameters taken from River Churnet are shown in table 1.
The copper concentrations ranged from 70µg/l to 90µg/l, with the mean concentration of copper
from all samples (80µg/l), >1200µg/l lower than ATSDR (2004) drinking water standards (1300µg/l)
and >1900µg/l lower than UK drinking water regulations (2000µg/l) (WHO, 2011) (figure 4). The
concentrations of copper in the upstream samples were not significantly different to the midstream
samples (p = 0.07) nor the downstream samples (p = 0.45), implying there is no influence of copper
discharge between these sample locations.
Table 1: Average copper concentrations and water parameters. (Mean ± Std. Dev.)

Location Copper pH pH Conductivity Dissolved O2 Temperature

(µg/l) (lab) (field) (µs/cm) (mg/l) (˚C)
Upstream 70 ± 10 7.0 ± 0.1 7.9 ± 0.3 275 ± 50 10.5 ± 0.2 7.8 ± 0.7
Midstream 90 ± 10 7.1 ± 0.1 7.7 ± 0.3 244 ± 17 11.0 ± 0.1 7.7 ± 0.7
Downstream 80 ± 20 7.4 7.9 ± 0.2 308 ± 24 11.0 7.6 ± 0.7
Control 30 7.4 - - - -

Figure 2: Average copper concentrations in upstream, midstream and downstream samples.

The conductivity recorded in the field ranged from 275 ± 50 (µs/cm) to 308 ± 24(µs/cm), which is low
when compared to the range that can be expected in freshwater streams (100-2000 µs/cm) (SWRCB,
2002). Using Pearson’s correlation, there is no correlation between copper concentrations and pH,
temperature or conductivity. However, there is a weak positive linear correlation between copper
concentrations and DO (r = 0.55). It should be noted that the pH recordings in the field were more
alkaline than the recordings in the lab, showing there were fluctuations in the accuracy.