BSC Dissertation: Environmental Assessment of Soil Quality at The Former Tomnadashan Copper Mine.

1
BSc (Hons) Laboratory dissertation:
ENVIRONMENTAL ASSESSMENT OF SOIL QUALITY AT THE FORMER TOMNADASHAN COPPER MINE
By Malcolm Alexander Sutherland (matriculation no. 9805423)
This report was submitted in partial fulfilment of the BSc. (Hons) degree in Environmental BioGeoChemistry, University of Glasgow, Monday 8th April 2002 REVISED IN JUNE 2013 (figures and appendices have been scanned)
Environmental Assessment of Soil Quality at the former Tomnadashan Copper Mine Copyright 2013 of LabSearch, a working title of Dr Malcolm Sutherland
CONTENTS
ABBREVIATIONS SUMMARY 1: INTRODUCTION 2: MATERIALS and METHODS

2.1 2.2 2.3 2.4 2.5 Field visit to Tomnadashan Soil properties and composition Total copper extraction Analysis of copper fractions Mineralogical analysis
page 3 page 4 pages 5 - 7 pages 8 - 24

pages 8 - 11 pages 11 - 13 pages 14 - 16 pages 17 - 20 pages 21 - 24 pages 25 - 38
Graphs 1 through 14
3: RESULTS and DISCUSSION

3.1 Experimental Data 3.2 Statistical treatment of data 3.3 Discussion
pages 39 - 60
pages 39 - 45 pages 45 - 56 pages 56 - 60
4: CONCLUSIONS and RECOMMENDATIONS ACKNOWLEDGEMENTS REFERENCES APPENDICES

Appendix 1 Appendix 2 Appendices 3a - 3d Appendix 4 Appendix 5 Appendices 6a - 6b
pages 61, 62 page 63 pages 64, 65 pages 66 - 84

page 66 pages 67 - 69 pages 70, 71 page 72 pages 73 - 80 pages 81 - 64
ABBREVIATIONS
% Total Cu Organic-bound
The percentage of total copper being plant-available (Graph 6) The copper fraction obtained using the H2O2-ammonium acetate extraction procedure The copper fraction obtained using the hydroxyl-ammonium chloride Extractant The copper fraction obtained using the acetic acid extractant Exchangable copper Oxide-bound copper Organically bound copper Remaining copper extracted using aqua regia Copper extracted using this extractant (see % Total Cu) The relevant data of EDTA-extractable copper for the (BCR) samples used in the sequential/separate extraction methods The percentage of the sum of all 3 extracted copper fractions which are exchangeable The percentage, of the sum of all 3 labile copper fractions, being held by oxides The percentage, of the sum of all 3 labile copper tractions, being held by organic matter (see %Total Cu) Loss-on-Ignition values for the samples used in the BCR separate/sequential extraction methods
Oxide-bound
Exchangeable Series 1/Step1 Step 2/Series 2 Step 3/Series 3 Residual EDTA Cu %edta EDTA for BCR
%step1
%step2
%step3
%EDTA BC LOI for BCR
SUMMARY
A laboratory project was carried out to analyse the impact of copper mining at Tomnadashan. This was an initial environmental assessment, which involved collecting soil samples from the abandoned site and some exposed mine waste. The primary objective was to study the levels and forms of copper which persisted in these samples, and mainly to assess its potential toxicity and availability. 2 transects were surveyed: Transect 1 (crossing in front of the mine), and Transect 2 (located where a smelter is said to have existed). Some stream sediment was also sampled. Total; plant-available (extracted using EDTA); exchangeable; oxide-bound; organically complexed; and, mineral-bound copper was analysed. Copper levels were compared with organic matter (determined by loss on ignition), soil pH, and levels of 4 other heavy metals (Mo, Ni, Pb, Zn) which also occurred within the copper porphyry at Tomnadashan. Levels of total copper, even in natural peaty soils, are generally above 100ppm, which partly reflected the unique chemistry of the underlying geology. However, at one end of Transect 2, with the river sediment and 2 selected mine waste soils, levels of copper far exceed 1000mg/kg. However, this trend was not seen with plant-available copper, nor with the other 4 heavy metals analysed. Levels of plant-available copper along Transect 1 were not significant (usually 20 - 60mg/kg), nor were they affected by the local mine waste. Plantavailable copper occurred at around 200mg/kg at the mine waste, and concentrations ascended from ~30mg/kg to that level along Transect 2. Nevertheless, the levels of potentially plant-available copper (exchangeable, or bound to oxides or organic matter) ranged between 100 and 250mg/kg along Trajectory 1, and occurred from 100 to over 500mg/kg along Trajectory 2. These levels were as much as over 3000mg/kg at the mine waste. The river sediment was also heavily polluted with copper, with potentially plant-available copper levels exceeding 2500mg/kg. In general, most of the Tomnadashan soils which were analysed contained moderate levels of copper, both in its total, and in its potentially phytotoxic forms. In localised areas, its potential phytotoxicity may be a cause for concern, and further investigation is recommended, particularly into where else this pattern may be occurring.
1: INTRODUCTION
1.1: Location
Tomnadashan is located halfway along the south bank of Loch Tay, Perthshire (east of Ardeonaig (N56: 30:07; W4: 09:15). The area is generally uninhabited, with rough grazing being the only land use, and access to the former mining site is only via a narrow minor road which follows this side of the loch. Geologically, the site is much more significant, with enriched veins and disseminations of copper and pyritic ore, along with other heavy metals such as molybdenum.
1.2: Mining Activity at Tomnadashan

During the early 19th century, the awareness of this porphyry at Tomnadashan encouraged initial mining tests to be carried out. It is said that a smelter was also raised slightly further downhill. Lord Brealdabane, who was ambitious in his aim to convert this into a significant copper-producing business, tried in vain over a few decades to make this become a profitable site, in one way or another. Copper ore extraction and treatment was initiated, but without success. A smelter was raised, and in the end, some copper was actually sold. Allegedly, phosphate was extracted and used for fertiliser production. Sulphur production was another practice which also failed, using the local pyrite source. Today, only a set of derelict cottages, and a small incision into the bedrock with an equally insignificant mine waste tip marks this historic location. The smelter downhill no longer exists, and, apart from a raised ledge structure seen up the slope, the whereabouts of each building and structure depicted in the 1861 O.S. map (Appendix 1) are questionable (Tomnadashan - a Re-examination; see References).
1.3: Environmental Implications of Mine Waste and Smelters

Typical concentrations of copper in soils above granitic parent material are usually below 20ppm (White, 1998). However, as Tomnadashan is located at a copper porphyry, the natural copper levels are likely to exceed this margin. The concern for, and investigation of these are firmly established today. Acid mine drainage is a common issue associated with mine waste (especially "slag" heaps), uniting both coal mining with non-ferrous extraction. A clue to this lies in the fact that copper porphyries, although highly enriched in iron, cannot serve as an iron ore resource due to the Fe being found as pyrite (FeS). The sulphur presents a potential lexicological hazard to both soils and vegetation alike due to its oxidation under weathering (Barnes, 1988; Kontopoulos et al, 1995; Radojevic and Bashkin, 1999): 2FeS2 + 7O2 + 2H2O 4SO42- + 2Fe2+ + 4H+
The resulting acidification is both deleterious, especially to aquatic life, and any subsequent chemical reactions (e.g. the reaction with metal sulphides) will degrade both soil and water quality. The visible mine waste at Tomnadashan is not copious- However, according to the old map (Appendix 1), the extent of mine waste seems to have been far more extensive, compared to the few square metres of un-vegetated waste seen today. Smelting, particularly of phosphate, is (and was) performed using sulphuric acid digestion, and thus, a local source of S is required (making pyrite a useful commodity to this end) (Barnes, 1988). During the mid-19th century, phosphate was becoming an important fertiliser (Tomnadashan - a Re-examination, 2000). Smelters, especially older designs, release particulates which are deposited onto the soil in their vicinity, and thus metal concentrations may become enriched in soils, with proximity to the site (Karczewska, 1996). Environmental standards not only apply to the condition of former mine waste heaps, but to the levels of metals being concentrated and dispersed into the surrounding soil and vegetation. The Environmental Quality Criteria (EU) which provides a table of MACs (Maximum Admissible Concentration) gives a spectrum of levels 10 be acknowledged, rather than a set list of numbers; this may be due to natural variations (e.g. geology) in soils being considered. For this project, cadmium, copper, nickel, lead, and zinc are considered, although copper is the main issue (Table 1):
Table 1: the Environmental Quality Criteria (EU) guidelines for metal concentrations in soils (this was relevant in 2002)
In reality, the use of total levels does not adequately reflect the actual toxicity which the metal may present. At present however, the complex variation of methods used to analyse available fractions of metals has yet to be harmonised, before a more useful table of limits is produced (Rauret, 2000).
1.4: Aims and Objectives

As the first environmental survey of Tomnadashan, the study on the distribution and behaviour of copper in soil samples collected from the site is an appropriate starting point.
All chemicals, reagents and instruments used are listed in Appendix 2. The aims behind the report are summarised:
To discuss findings on the levels (and possible toxicity) of copper, and some associated metals, in relation to the mine waste, and the smelter. To investigate whether or not the mine waste is largely buried, and may be producing leachates alone with heavy metals, passing downhill. To investigate the forms of copper which are present, and the environmental implications suggested by the findings. To evaluate what strategy is required in the further study of copper (or other metals) distribution at Tomnadashan.
2: MATERIALS AND METHODS

2.1: Field Visit to Tomnadashan
The Abandoned Mine This is characterised by a hollow in the hillside. The mine appears as nothing more than a small cave; a small heap of mine waste is found nearby down the gully, covering only a few tens of square metres (Figure 1):
Figure 1: entrance to the copper mine, Tomnadashan, near Loch Tay
Pyrite, which is characterised by the tarnished golden brown colour and occasionally brilliant yellow cubic crystals, is either smeared as fine scales across the rock, or disseminated within fractures. Pyrite rarely appears in its native crystal form due to weathering (Barnes, 1988), which makes Tomnadashan geologically unique. Molybdenite (MoS2), chalcopyrite (CuFS2), galena (PbS) and quartz (SiO2) also occur (Plant et al, 1983). Collecting the Soil Samples As shown on the map in Figure 2 over-page, 2 trajectories were covered. Trajectory 1 crossed in-front of the mine. Trajectory 2 was conducted at the area where the Jefferies' acid plant may have stood. The top 10-15cm of the soil profile was dug out using a spade, with samples taken from the top 10cm (except for one sample, where samples from the top 5cm, 10cm, and 20cm depth were taken at site T1 S8 (Trajectory 1, Sample 8). At the start of each trajectory, a double compass bearing was taken to locate the starting point on the map. All along the trajectory, the compass bearings between each sampling point was recorded, and the distance in paces noted (around 26paces per 20m by the author). The spade was cleaned of soil after each incision at every site. For the 3 samples taken where the acid plant may (not) have stood, an auger was used instead (and also cleaned after each incision).
Observations made during Sampling Trajectory 1 and the Bing Undisturbed rough grass and heather was seen between sites T1S1 and T1S3. At T1S4 this gave way to thin grassy topsoil as the gully in front of the mine was approached. The T1S5 and T1S6 soil samples were taken within the gully, not far from the exposed waste bings (Figures 3a, 3b, over-page). T1S7 to T1S9 soils were taken further east, past the gully, and the T1S10 sample was taken in the adjacent field. Thin grass covered the trajectory between T1S4 and T1S8, before the return to longer grass. The soils along the trajectory ranged from dark brown, peaty and root-dominated (at either end of the trajectory), to poorly developed, light brown stony soils, particularly within the gully Trajectory 2 The short trek from T2S1 to T2S5 crossed into a small watershed alongside the row of trees (see 'nap), where some waste rock was seen. Long grass (seen at T2S1) gradually gave way to bushes as the ground became increasingly waterlogged. The T2S4 and T2S5 samples were taken behind the raised structure (T2S5 was taken nearby the river). The soils were generally darker, peaty and water-saturated around the watershed.
10
Figure 3a: the small rock waste mounds in front of the mine. Figure 3b: field notebook placed on poorly developed soil taken for the West and East Bing samples.
Taking the "Building", Bing and River Samples The raised structure appears as a grass-covered ridge where the smelter may have stood. The building samples were extracted using a soil corer (Figure 4); soils taken from here were strongly decolorised, characterised by orange, brown (even pale yellow colours), thin root penetration and a fine sandy texture.
Figure 4: the soil corer
A thin coating of premature soil exists along the top of the bings, due to chemical breakdown of the rock fragments. The bing samples were taken where no vegetation had
11
yet colonised the exposure. The river sample was collected where the water emerges further downhill, in a small pond filled with fine gravel.
2.2: Soil Properties and Composition

Observed soil properties Shortly after being collected in the field (before being transported back to the Chemistry Department, and stored in a windowless, refrigerated room (the "cool room")), aliquots of soil from each sample were taken and described, as shown below and on page 12:
Properties of oven-dried soil aliquots

Grab-sampled soil broken up. Taken at random from original soil in bags. Oven-dried overnight at 105C. Soil structure often dominated by roots, esp. with peaty soils mine.
T1S1: medium greyish-brown colour. Roots dominate soil structure, with smaller clusters of rootlets holding small lumps of soil together. Coarser coagulated soil lumps and roots removed by sieving. T1S2: medium greyish brown. Rootlets coagulate large lumps of soil together. A few small rock fragments. T1S3: pale orange-brown. Some > 1cm rock fragments (metamorphic). Small narrow rootlets seen. More even distribution. T1S4: medium brown. Some large (>Imm) rootlets. Some large metamorphic rock fragments (>1cm). Poor sorting. T1S5: pale brown. Dominated by rootlets, coarse quartz fragments, pyrites and metamorphic rock fragments (some > 1cm). T1S6: orange brown. Roots narrow (<0.5mm). These coagulate the soil. Small rock fragments (<1cm). T1S7: pale orange-brown to medium brown soil. Some large (0.5 to 1mm width) rootlets present. Some rock fragments (occasionally >1cm) seen. T1S8: dark brown. Roots (0.5-1mm wide) hold soil in clumps. Roots, some coagulated soil lumps and some small quartz pebbles removed ay sieving. T1S8 (Sub.)*: paler orange-brown. Some large metamorphic rock fragments (removed by sieving, comprise quartz also) present, poorly sorted. Some pyrite set;-'. T1S8 (Org.): peaty, dark brown, small rootlets surround soil clumps. Few significant rock fragments. T1S9: medium brown soil with few roots. Some large pebbles (1 to 3cm, metamorphic). Coarse fraction dominated by rock fragments. T1S10: roots present- aggregate comprises much of the soil. Dark brown soil colour. Wide size distribution. Roots, some small (circa 1cm) rock fragments (such as quartz), and coagulated soil lumps sieved out. T2S1: medium greyish brown soil. Roots (circa 0.5mm) hold small clumps of soil together, These, along with some small quartz and metamorphic rock fragments, removed by sieving.
12
T2S2: medium-pale orange brown. Soil significantly coagulated. Rock fragments persist. T2S3: dark/medium brown soil. Roots present. Rock fragments mostly insignificant (<1cm). T2S4: medium pale to dark brown. Roots dominate and clump soil together. Rock fragments (<1cm) adundant, including some quartzes and pyrite. T2S5: variation from orange-brown to peaty dark brown. Roots dominate, with some large pebbles (1 to 3cm). West Bing: Pale to orange brown rock fragments dominate - poor soil development, no roots seen. Very poorly sorted sediment. East Bing: poorly developed soil. No roots. Similar rock fragments to that seen in the West Bing. Very poor sorting. Some >3cm pebbles. Orange-brown colour overall. River: Roots seen. Sediment grey to brown overall. Contains pyrite, quartz and weathered ferrous rock fragments (medium brown). B1: sticky granular texture. Roots and rock fragments absent. Strong orange colour. B2: (as above) B3: (as with B1 and B2) * Sample taken from subsoil horizon, below the dark brown, peaty, organic-rich topsoil Sample taken from top 5cm of soil, which appeared organic-rich (hence the abbreviation "Org.")
Organic matter (as determined by Loss-on-Ignition) (Appendix 6a) Several methods of analysing for organic matter are proposed. The loss of ignition is a method which has also varied, and the ignition and interference of carbonates is often an issue, although more so with neutral and alkaline soils (Heiri, 1999). Carbonate melts at around 800C, whereas the furnace is set at 550C. In light of this, the acid digestion and drying prior to furnacing was omitted. Soil samples were oven-dried and dessicated to remove moisture. Their glass beaker containers were gently shaken to improve homogeneneity, and 1g triplicates were weighed out using an analytical (4 decimal place) balance immediately after removing from the dessicator into silica basins. These were initially labelled, then laid out in rows, with their order being recorded. They were then placed into the furnace, and heated for 6 hours, before being left to cool down overnight. The following morning, these were taken out of the furnace, and placed in the oven for an hour, and then into the desiccator in order to eliminate any moisture regained after furnacing. These were then weighed out again in the same manner as before (basin weighed out immediately after being taken out of the dessicator).
13
Soil pH (Appendix 6b) In general, a sample of fresh soil is immersed into distilled water, shaken for around 15 to 20 minutes, allowed to settle to the base of the container, and the water is then analysed using a pH probe (usually a calomel electrode). Differences arise, as to what ratio of soil (mass) to water (volume) is prescribed (Bashkin and Radojevic, 1999). In this instance, a ratio of 4g of fresh soil (taken from the "cool room"), to 10mL of water was prepared. This was not a precise measurement: a 50mL measuring cylinder was used for the water, and the 2-decimal weighing balance was used for the soil (to obtain 4.00g). This was performed using groups of 4 samples at a time (to reduce delay in measurements and lime for shaking). Once the soil and water were emplaced inside the glass jars (Figure), these were intermittently shaken over around 15 minutes (this also is not entirely precise). The calomel electode used was calibrated to pH4 and pH7, as recommended. Air-dry soil moisture (Appendix 6c) Fresh soil was shaken, before a sample was taken out using a hand shovel, and placed onto plastic sheets laid out on the laboratory bench which was not exposed to sunlight. Between obtaining each sample, the shovel was cleansed using distilled water and dried. The soils were then left to dry. This could take as long as 3 days, as some samples were derived from peat soils. Once dry, they were then sieved through a 2mm mesh, and the coarse fraction was discarded. Approximately 2 grams of soil were weighed out precisely, to 4 decimal points. The beaker into which it was placed was initially weighed. (Beforehand, the beakers were placed into the oven for about 2 hours, and placed into a desiccator using longs, in order to eliminate moisture.) Each sample was weighed out in triplicate. They were then placed into the oven (set at circa 105C), and left overnight. The next morning, each beaker with its soil was transferred into as desiccator using tongs (so as not to contaminate the surface). As was done with the beakers on the previous day, each one (with its soil in this instance) was immediately weighed precisely, by taking it out from the desiccator using tongs, before closing the desiccator lid. The calculations used for air-dry soil moisture are provided:
The problem in applying this to the exact samples being analysed for specific copper fractions, is that they cannot be pre-heated in order to analyse their moisture, as this would alter the nature by which copper is held within those samples.
14
2.3: Total Copper Extraction

Acid digestion methods such as nitric and aqua regia, extract the "total" copper present in the sample, although this may not scavenge all mineral-based copper (that within the crystal matrix of sulphides or rock fragments) (Bashkin and Radojevic, 1999). Acid digestion (Appendix 6d) Preparation of samples and solutions, along with digestion and filtration, was all carried out in the fume cupboard. Concentrated nitric acid (69% soln.) and aqua regia (prepared using 200mL of concentrated nitric acid, and 600 mL of 1:1 (HCl: distilled water)) were the reagents used in this preparation. 0.5 grams of oven-dried soil of each sample was weighed out accurately, then inserted into the long lubes used for block digestion, using a small plastic scoop connected to a pipette (nick-named the boat). The scoop was then brushed of remaining soil dust before being used for the next sample. 10mL of acid in a 50mL measuring cylinder was then dispensed into the tubes, which were then placed as a rack on the digestion block. This was set to 120C, and the tubes were left to boil for 4 hours, before being raised out and left to cool down for 30 minutes. These were then filtered using 54 Whatman filter paper, collected in 50mL volumetric flasks, and made to the mark using distilled water. Sources of error in the preparation stage can have very significant implications on the results obtained (Skoog, West and Holler, 2000). The incomplete extraction of heavy metals, volatilisation of the solvent, evaporation, along with contamination within the acid and the tube walls, will contribute to this. All glassware was cleaned for over 24 hours in Decon solution, before being rinsed 3 limes with tap water, and another 3 times with distilled water. Another important source of error is the difference in mass of the weighed-out sample, and that which actually enters the tube. The scoop was placed back on the balance before being brushed, to account for this difference in mass, which could be as much as 0.005 grams (around 1% of the sample). Preparation of standards used for total metal analysis If a solution prepared from the 1000ppm [Metal] standard stock solution was to be dispensed to prepare standards, its volumetric flask was capped, and inverted each time prior to its use, to maintain a uniform concentration. Cadmium (Cd) The linear range for this element is given as 2mg/L. For Cd, the standards prepared were 0.4, 0.8, 1.2, 1.6 and 2mg/L Cd solutions. A 4mg/L Cd solution was prepared by adding a 2mg/L aliquot of the 1000ppm Cd standard AAS stock solution, into a 500mL volumetric flask, which was then made to the mark with distilled water. The standards were prepared as shown in Table 2 over-page ("water" refers to distilled water):
15
Table 2: cadmium solutions prepared
Copper (Cu) The linear range for measuring this element using AAS is 5mg/L. 10mL of the standard Cu solution was pipetted into a 1L volumetric flask, which was then made to the mark, using distilled water. From this 10ppm [Cu] solution, the standards were prepared as shown, using aqua regia, to produce a similar matrix to that of the samples (Table 3):
Table 3: copper solutions prepared
Lead (Pb) The standard calibration involves the use of 4, 8, 12, 16 and 20 ppm Pb standards. 10mL of 1000ppm Pb was pipetted into a 500mL volumetric flask to prepare a 20ppm Pb solution. The 4 standards were prepared as shown in Table 4. As the 20prm Pb solution did not contain aqua regia, this could not be used for AAS due to matrix differences, which would affect the signal being monitored.
Table 4: lead solutions prepared
16
Nickel (Ni) A 10ppm Ni solution was prepared from the 1000ppm standard AAS solution, by pipetting 5mL into a 500mL volumetric flask, before making it to the graduation mark using distilled water. The procedure for preparing the 2, 4, 6, and 8ppm Ni standards are similar to that for lead (above), in terms of volumes of diluted Ni solution, and aqua regia being used. As with Pb, the 10ppm Ni "top standard" solution could not be used. Using a top standard of 8ppm produced a greater absorbance signal. Molybdenum (Mo) The linear range for this element is 40mg/L. To prepare a solution of this concentration, 20mL of 1000ppm Mo was added to a 500mL volumetric flask, which was made to the mark using distilled water. Again, the ratio of distilled water to the volume of aqua regia follows the same pattern as for Ni and Pb (in this case, the standards are 8, 16, 24 and 32ppm Mo). Zinc (Zn) The linear range for Zn is 1mg/L. A 2ppm Zn solution was prepared by pipetting 1mL of the 1000ppm standard AAS solution into a 500mL volumetric flask. The preparation of the 0.2, 0.4, 0.6, 0.8 and 1ppm Zn standards follows the same pattern as for the copper standards. All 5 standards were used. Blanks 3 blanks were prepared along with the acid digestion samples during the experiment, and made to 50mL with distilled water. These are listed beneath the AAS results for total copper and other heavy metals in Appendix 5. Likewise, blanks were prepared for all experiments which included analysis of copper using AAS. Converting leachate Cu levels to Soil Cu levels The calculation used for all AAS-based calculations is provided below:
17
2.4: Analysis of Copper Fractions

Copper in soils is accommodated mostly by plants, organic matter and inorganic surfaces; very small proportions of copper remain in solution. Under natural conditions, copper in soil originates from the weathering of copper-bearing minerals. Copper then enters into organic and inorganic complexes; it may be adsorbed onto precipitated solid surfaces, diffuse into soil minerals, or be absorbed by plants, microorganisms and animals:
Figure 5: movement and phases of copper in soils (taken from White, 1997)
Copper (and any other metal) will never simply be transported from soil to plant. Because of this, a total copper value doesnt provide enough information on the actual toxicity presented by the metal. Ethylene-diamine-tetra-acetic (EDTA) acid extraction This is used for analysing the "plant-available" heavy metal in soil, i.e., that which can be brought into the soil solution and quickly incorporated into the rhizosphere. The procedure used was taken from the protocol given under Method 26 of The Analysis of Agricultural Materials (MAFF: RB427). 14.60 grams of EDTA salt were weighed out onto a 2-decimal weighing balance using a clean plastic spoon (stainless steel spatulas are discouraged by Skoog, West and Holler (2000) due in possible metal contamination). 950mL of distilled water were added into the volumetric flask. 8mL of concentrated (37%) ammonia solution were added to this in the fume cupboard, and more distilled water was added up to the graduation mark. Dissolution of the salt could take as much as 15 minutes by inverting the flask. 10 g of air-dried soil was weighed out, and placed inside a glass jar, wherein 50mL of the EDTA solution (at about pH7 0.1) was pipetted. The jars were placed on the revolving
18
shakers for an hour, and the solvent was then filtered using No.2 Whatman filter papers (closest equivalent to No.40, as specified by MAFF). The Standardised BCR Sequencial Extraction This method determines three phases of copper: (1) readily exchangeable Cu; (2) oxidebound Cu; and, (3) organically complexed/chelated Cu. A residual fraction (the less readily ayailable, mineral lattice-bound Cu) was also analysed. Introduction In addition to a sequential extraction method prescribed by Rauret et al (2000), samples were also individually extracted using one of the 3 extractants. This arose due to difficulties in decanting the filtrate after centrifugation, although a technique for this was developed, which allowed some samples to undergo all 3 extraction methods. For each extraction stage, the extractant added is equilibrated with the soil, by shaking the mixture for several hours. The treated soil should he physically separated from the leachate, when placed onto the centrifuge machine (which is set at 3000g, for 20 minutes). The liquid fraction should then be decanted into a container. As many samples chosen were organic soils, very fine particles were easily dispersed into the liquid fraction once the centrifuge bottles were removed from the machine, which made decanting, without losing some of the soil impossible. With care taken not to shake the bottle whilst gently removing it out of the centrifuge machine, and when holding the bottle down whilst unscrewing me lid (to minimise disturbance of the soil/water column), a moderately clean liquid could be dispensed. However, at least a few mL of liquid had to remain as the angle of tipping the bottle reached a critical stage, when the soil began to advance towards the neck of the bottle. The liquid collected inside a polyethylene bottle was immediately filtered using Whatman No.50 paper, before being made to the mark in its volumetric flask, and stored in the cool room. This experiment did not involve every soil collected at Tomnadashan. 12 soils were chosen, with the second trajectory (T2) being the primary focus. All T2 sites were chosen. The West and East Bing and River samples were selected. The B1 to B3 sites were not chosen due to limited soil supply. Sites from the first trajectory included T1S1 (a normal soil for the area); T1S4 (in front of the mine); and both the T1S8 (Org), and T1S8 (Sub) soil, in order to compare the copper fractions obtained, with soil organic matter. Stage 1 (Step 1) The extractant solution required was 0.11 mol/L acetic acid. This was prepared from glacial (pure) acetic acid in the fume cupboard. 25mL of this was pipetted into about 500mL of disriiled water in a glass beaker, which was stirred, before being poured into a 1L glass volumetric flask, before being made to the mark with distilled water.
19
This was then stoppered and inverted, before 250mL of this was pipetted (using 100ml and 50mL pipettes) into another 1L glass volumetric flask, which was also made to the mark using distilled water. Approximately 1g of soil was weighed into each bottle, using the 4-decimal point weighing balance. 40mL of acid was added to each sample using a burette, before the bottles were tightly sealed, and placed onto the 30rpm soil shaker for 16 hours (overnight). Next morning, centrifugation, decanting and filtration were performed as described. After decanting, 20mL of distilled water from a burette was added into the centrifuge bottles, which were put on the shaker for an hour and centrifuged for 20 minutes, before the waste water was then decanted and disposed. Stage 2 (Step 2) On the same day, the extractant for this step was prepared. 34.75g of hydroxyammonium chloride way weighed out on an Oertling JC-12 balance using a plastic spoon, before being dissolved into (approximately) 400mL of distilled water. This solution was then transferred into a 1L volumetric flask. 25mL of 2M nitric acid was pipetted into this, before the solution was made to the mark. To prepare the 2M acid, around 128mL of concentrated nitric acid was used, and poured into a half-full volumetric flask of distilled water, before being made to the mark. Both flasks were sealed, and inverted, prior to their use. The acid solution was prepared in the fume cupboard. Rubber gloves were used during the preparation of both solutions. 40mL of the extractant was added via a 50mL burette to the 1g of soil, which was weighed out using the 4 decimal-point balance. The soil mixtures were collected into glass jars, which were put on the rotating shakers overnight (16 hours). The next morning, these were filtered using Whatman No.50 filter papers, and the filtrate collected in the 50mL volumetric flasks (made to the mark using distilled water) were transferred into polyethylene containers, and stored in the coolroom prior to analysis. Stage 3 (Step 3) 2 solutions were required for this extraction. Solution "C", which was concentrated hydrogen peroxide, was used by the authors (Rauret et al). However, due to the high organic content of some of the soil samples, the possible violent reactions and loss of sample was averted, by diluting the 8.8 mol/L H2O2 to a fifth of its concentration. 50mL of the concentrated solution was pipetted into a 250mL volumetric flask containing about 100mL of water, which was then made to the mark, capped, and inverted prior to use. Solution "D", a 1.0 mol/L solution of ammonium acetate, was prepared by dissolving 77.08g of the salt (weighed out on the 2-decimal point balance) into 800ml of deionised water in a 1L glass beaker in the fume cupboard. This was passed into a 1L volumetric flask through a filter funnel inserted at the top to prevent spillage. This solution had to be established at pH2 ( 0.1) using a calibrated pH meter, this adjustment was performed in the fume cupboard using concentrated nitric acid, which was added in aliquots, using a plastic
20
pipeline. Once at around pH2 (the actual pH was 1.93), the solution was made to the 1L graduation mark with de-ionised water, capped and inserted prior to use. Had this; experiment been performed according to the journal, 10mL of solution C would have been added to the remaining soil residue after Stages 1 and 2, in a centrifuge tube. Instead, 1g soil aliquots were weighed out in duplicate into glass jars, and 10mL of Solution C was pipetted into these in the fume cupboard, before the jars were capped loosely using polyethylene screw-caps. These were left to digest in the fume cupboard (at room temperature) for an hour, whilst being occasionally shaken to allow the soil to equilibrate with the solution. Meanwhile, 2 water baths were heated, whereby the temperature, using the dials, was raised to around 85C; in reality, the temperature did not exceed about 75C. The samples were then placed onto the water baths, and left for an hour with their caps intact (and were occasionally shaken during the first 30 minutes). Thereafter, the caps were removed, and the solution was allowed to evaporate until around 3mL remained, before another 10mL of Solution C was added to each sample. These were capped again for an hour (shaken occasionally for the first 30 minutes), before being allowed to evaporate until a slimy residue remained. (Rauret et al instructed the analyst to "reduce the volume of liquid to about 1mL" due to the diameter of the jar; this is difficult to predict as the samples were not allowed to evaporate to dryness, as instructed.) 50mL of Solution D was added to this, and the jars were then tightly capped, before being placed on the shaker for 16 hours. Thereafter, the leachate was filtered using No.50 Whatman filter papers, collected into a 50mL volumetric flask, made to the mark, and capped, before being taken into the cool room for storage. The Residual Copper Once these 3 fractions of copper had been extracted, the centrifuge bottles. After decanting the Step 3 extract, were rinsed, by adding 50mL of distilled water via burette, and shaking fur an hour, centrifuging, and then disposing of the water. Here, another alteration was made to the method of analysing the remaining sediment: instead of adding aqua regia in situ, as much of the sediment as possible was transferred out of the bottles, and into glass beakers. These were then oven-dried, and 0.1 gram portions were weighed out to 4 decimal places, before being transferred into the lung tubes used for the block digestion. 10mL of aqua regia was added, and the samples were left to equilibrate over-night. The next morning, the tubes were placed on the digestion block for 4 hours, before being left to cool, and the samples filtered using No.50 Whatman paper. As with total copper, the filtrate collected was made to 50mL in volumetric flasks, and stored in room temperature conditions prior to AAS analysis.
21
2.5: The River Sediment

Mineralogical Analysis of River Sediment using XRD In the simplest terms, the instrument shown in Figure 6 records the intensity of X-rays reflected off the surfaces of crystals and mineral powders (Walker, 1995). The angle at which radiation is transmitted onto the surface is critical, as the the X-rays will be deflected by the crystal structure of the mineral, when approaching at a fixed angle. The river sediment sample alone was selected, mainly due to its low organic content, but also as the river drains out from the slope below the waste rock. It was anticipated that some of the minerals present in the sediment may have originated from the waste rock, or that sulphides present within the soil due to the underlying geology, may exist. 2 samples were taken from the oven-dried, sieved river sediment. The first was a random sample taken after shaking the soil bag; the second consisted of crystals and small rock fragments, which were chosen in order to determine some of the sulphides present. The samples were ground into powder, using a small (hand-held) mortar and pestle, which were treated with acetone to produce a slurry. This was performed to enable the sample to be poured onto the slide. The slurry was flattened out on the slide using a clean blade to form a very thin but opaque layer with its thickness almost indistinguishable.
Figure 6: the XRD instrument used for analysis of river sediment samples (Phillips PW 1050/35)
The slide was inserted onto a clip beneath the centre cap on top of the XRD machine, and the X-ray port was then switched on for around 55 minutes, using the computer software which operated the machine. Afterwards, the slide was taken out, and the data collected on the computer was used w produce a qualitative chart, on which the number of counts per
22
minute (a measure of the X-ray radiation reflected by the sampler was plotted against the angle of the radiation striking the sample surface (see Appendix 3). Analysis of copper in particle size fractions 2mm, 0.5mm, 0.25mm, 0.125mm and 0.63mm mesh sieves were used, to give a general overview of the particle size distribution itself. These were fitted on top of one another with a collecting basin at the base, with the order of mesh size increasing upwards. About a quarter of the fresh river sediment had been scooped out, and air-dried, before being transferred into a heavy duty plastic bag. The contents were poured onto to 2mm mesh sieve at the top of the sieve stack, and the entire stack was then shaken before and after each sieve was removed, with the retained contents brushed into a wide plastic container. Each fraction collected into the container was weighed using a 1-decimal point balance (as a large quantity of the sediment was provided), after which the container was scrubbed clean using a brush and paper towel. A portion of each fraction was transferred using a plastic spatula into a small glass beaker (except the <0.iyi1mm, and >2mm fractions). Triplicate 1g aliquots of the (0.063 to 0.125mm), (0.125 to 0.025mm), (0.25 to 0.5mm) and (0.5 to 2mm) fractions were weighed out using a 4 decimal-point balance, each into another small (50mL) glass beaker. 10ml of concentrated acid was poured onto this in the fume cupboard, using a plastic 10mL measuring cylinder. The beakers were left over a weekend for the acid to fully equilibrate with the sediment. The following Monday, these were placed on the hotplate in the fume cupboard and heated to 110C for 4 hours, and then left to cool for another hour. The extracts were filtered in the fume cupboard, using No.541 Whatman filter paper (a faster method in comparison to using No.50 paper), and collected in 50mL glass volumetric flasks before being made to the mark with distilled water. These were analysed for copper using the AAS method, using the aqua regia calibration standard solutions (as these contain nitric acid. hence a similar matrix will exist).
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
3: RESULTS AND DISCUSSION

3.1: Experimental Data
(Although all tables of triplicate values are given throughout Appendix 5, the graphs are all contained between pages 23 and 38. Some of the terms used in the data are explained under Abbreviations.) Baseline data and conversion factors This includes lists of the masses of soil aliquots and their containers, calibration charts, and results taken down during usage of the AAS facilities. The data presented in this chapter is the final product of both the measurements taken, and the necessary calculations applied. The baseline data is presented in Appendix 5 along with the results discussed. The conversion of calculated concentrations of copper, from that in air-dry soil, to oven-dry soil levels is calculated for the results obtained for samples treated with EDTA, and the sequential extractants. The calculation is given:
Baseline data for calculating the moisture content of the samples is given in Appendix 5a. Total Copper levels Average values (Graph 1; Appendix 5c) The most obvious feature is the outstanding contrast between Cu levels in the T2S5, bing and river samples, compared to the other sites. This does not appear to influence sites T1S4 to T1S7, which are proximate to the bing sites by a few metres. It can be concluded from this that copper-containing dust being wind-blown from the exposed waste does not pose a particular threat to the surrounding soil. Both T2S5 and the River samples show much more elevated copper levels, which suggests that contamination could be spreading downhill by infiltration, possibly from a local source (the 1861 map shows waste covering all the area between the mine and the smelter). The second point to note, is that most samples show levels in breach of the EC standards (of max. 140mg/kg Cu in dry soil), even the natural soils such as T1S1 and T1S10 show levels above 100ppm, which may owe to the soil resting above a copper porphyry. Replicate aqua regia extraction values for total copper (Graphs 2, 3a, 3b) Graph 2 shows the variation in levels across Trajectory I. There appears to be a moderate increase towards the centre, although the replicate values also tend to spread apart from
40
one another (especially those ofT1S1). In terms of Cu having been extracted with nitric acid, levels between T1S1 and T1S3 exist at around 150ppm, then rise to over 400ppm towards T1S5, retreat sharply at T1S6 to 200ppm, then rise steadily towards T1S8, before decreasing to just under 20Uppm in T1S10. This pattern is reflected by the aqua regia-extracted Cu levels, although T1S7 shows a protruding value for one of its triplicates. On the whole, Cu levels soar mainly around T1S5, and are moderately elevated between there and T1S9. T1S5 exists within the gully in front of the mine and near the waste, and the high levels may reflect copper infiltrating thereto. Graphs 3a and 3b show copper levels across Transect 2. Graph 3a displays the values on a logarithmic scale - most triplicate values appear accurate, except for the B3 sample (where one value is noticeably lower). The steady increase in levels from T2S1 to T2S5 is shown by an exponential increase on Graph 3b (normal scale). Copper levels rise steadily from about 100ppm (perhaps a "normal" level) to those seen halfway along Transect 1 (around 400ppm), between T2S1 and T2S4. The higher the levels, the less agreeable the triplicate values; the bing samples show triplicates which vary by as much as a few hundred mg/kg. Other heavy metals (Graph 4, Appendix 5d) Graph 4 compares copper with four of the five other heavy metals analysed (as cadmium levels were negligible). This is depicted on a logarithmic scale as the relationship between Cu and metals such as Pb are known to relate in this manner (Ngriau, 1979). The comparisons are reasonable, although varied. Pb and Mo increase in conjunction with Cu from T2S1 to T2S5. However, Ni and Zn do not share this pattern. Some elevated Pb and Mo values are seen with the bing and river samples, and both show lower values with the "Building" samples. Ni and Zn show very low values for the "Building" samples, but levels are not elevated with the bing and river samples. Soil limit values With reference to Table 1, the levels of total copper nearly always (and sometimes far exceeded) the EC limit values of 50-140 mg/kg. Although levels of cadmium are negligible, it can be said that levels, even if exceeding 3mg/kg, only do so marginally. Levels of Zn and Ni are moderate, and generally do not exceed legal limits. Levels of Pb are nearly all below the 300mg/kg threshold, except at T2S5, where they have "shot up" to almost 1000mg/kg at that site exponentially (even on a logarithmic scale), from below 100mg/kg along the other sites at Trajectory 2. EDTA-extracted Cu levels (Graphs 5a, 5b; Appendix 5e) These are shown in Tables 4 and 5 in the appendix (but not in terms of oven-dry soil). Graph 5a shows the distribution of EDTA-extracted copper across Transect 1. The pattern is quite different to that for Total Cu. There does not appear to be a significant increase towards the centre of the transect; the only exception to the even spread of copper soil levels (circa 2025ppm) is at T1S8, due to the variation in extractable copper between the topsoil (T1S8 Org.) and subsoil (T1S8 Sub.). This sustained level may indicate that any past mining activities and present waste does not appear to seriously affect the availability of trace
41
elements in soils collected here. Graph 5b shows EDTA-extracted levels along Transect 2, at the waste bings, within the river sediment, and along the raised ground which may have been a building foundation. It should be borne in mind that only limited samples were taken at the raised ground, although the single values there show very low copper levels (circa 30ppm), which reflect the low levels for total copper at these sites (90-120ppm). However, there is less agreement amongst some of the triplicate data sets here. Those for T2S5 are dubious, with the possibility that the low value of circa 25ppm is not representative. Levels within the River sediment are also uncertain. The increase in levels between T2S1 und T2S5 appears certain, approaching levels seen with the bing and river sediment samples. This appears to suggest that the raised copper levels within the river sediment and at T2S5 (which are proximate to each other), may be influenced by a point source of copper. EDTA-extractable Cu and Total Cu (Graph 6) Graph 6 shows the proportion of Total Copper being plant-available ("%EDTA", i.e., the proportion of total copper extracted by EDTA). Compared to the (50 to 90%) values obtained by Schramel et al (2000), or the (60 to 80%) values obtained by Hogg et al (1993) using agricultural and forest soil, the (5 to 30%) values (except for an anomalous 63% at T2S4) are considerably lower. The graph also depicts the Loss on Ignition values as percentages. There appears to be some correlation between this, and the percentage of total Cu extracted by EDTA, particularly along Transect 1. An exception 10 this is seen with the "Building" samples, with moderate EDTA-extractable copper levels, in spite of almost negligible organic matter. It is also interesting to note that very low levels of plain-available Cu exist at the poorly developed soils at the bings, possibly since most of this material is inorganic, with Cu being retained within the mineral phase. Along Transect 1, the levels of EDTA-extractable Cu appear to decrease slightly towards the centre, although lower values occur in intervals (such as T1S5, T1S7 and T1S9). Along Transect 2, the extractable levels decrease between T2S1 and T2S5, although there are erratic variations along the transect. The sharp decrease between T2S4 and T2S5 may owe to the average value obtained for T2S5 being lower than it should (as one of the triplicate values is considerably lower). The organic-poor river sediment shows very low levels of EDTA-extractable Cu, which may also indicate that most Cu is contained in the mineral fraction, which would be unavailable to plants (White, 1998).
42
Copper fractions obtained using selective extraction methods (Appendices 5g, 5h) Comparison between Separate and Sequential extraction (Graph 7) The issue of poor reproducibility in sequential extraction experiments has triggered considerable debate in recent years (Rauret et al, 1998), with criticism on the methods themselves as being non-specific in which copper binding sites are targeted (Schramel et al, 2000). Caution should also be paid to the low number of samples used in the selective extraction procedure (4 sites, hence 12 replicates). Graph 7 shows the comparison between the separately, and sequentially-extracted Cu fractions in sites T2S2, T2S3, T2S80rg and West Bing. These four were chosen to represent small-scale changes along a transect (with T2S2 and T2S3), the influence of organic matter (TISSOrg.), and the influence of copper mine waste (West Bing). The most striking feature is the larger quantity of copper extracted sequentially throughout Steps 1, 2 and 3 (although this seems less important with Site T1S8Org.). The main contributor to this is the organic fraction (extracted during Step 3), which appears more successful, especially with the West Bing samples which were sequentially treated. This pattern is generally not seen with Step 1 (extraction with hydroxylamine chloride). As these levels are in air-dry values, the sites themselves cannot be compared. Overall, it appears that removing copper fractions in sequence is more successful. Whether this is due to reduced re-adsorption of copper back onto other fractions, or that other fractions present with the separate extraction soil samples influence the behaviour of the extractant itself, requires further investigation. Sequentially extracted Cu: results (Graphs 8, 9) Graphs 8 and 9 present the levels of fractions obtained by sequential extraction. As all 4 fractions put together should represent the total copper present in a sample, the fractions are presented as percentages of the total copper. Graph 8 shows the percentages of fractions of all replicate samples used in the sequential extraction. Although the variation in the proportions of exchangeable (Step 1), reducible (Step 2) and organic (Step 3) copper relate to one another, their increase occurs at the expense of the residual copper fraction. The organic complexation sites (in terms of copper-binding sites) are of primary importance (with the exception of the West Bing samples). This is understandable since the other 3 sites consist of peaty soils, which are enriched in organic matter which has accumulated, along with the trace elements it contains (White, 1998). Of secondary importance are the oxides, as shown by the fractions extracted in Step 2. These are particularly relevant with the T2S2 and T2S3 samples, but less so with the organic TISSOrg., and West Bing samples. Very low (<10%) levels of exchangeable copper appear to exist, although fractions are slightly greater with the T2S3 and West Bing samples; here the variation between triplicate sets is
43
noticeable, but not very significant. The residual copper fraction percentage levels show the most variation between triplicate values, especially with the T2S2 soil samples. As a result, it is difficult to deduce, what levels these may generally occur at with the four soils analysed, although it appears certain that residual copper is more important at the West Bing. In spite of the variations discussed, the average distribution of copper fractions is shown on Graph 9. The freely exchangeable copper is insignificant, with the vast majority of copper cations being bound to specific sites within the soil, and this may be reflected by the small proportions of total copper present being extracted by EDTA. There is considerable variation in the copper held by oxides, as indicated by that seen between sites T2S2 and T2S3, although it may be suggested, that this fraction is less significant with sites affected by mine waste (West Bing). The organic-bound copper appears to vary positively, in relation to organic levels in the soil. Separately extracted Cu fractions: results (Graphs 7, 10, 11, 12) The great drawback in performing separate extractions is that a residual value cannot be obtained as other fractions will account for it. Although there were differences between the total sum of levels produced, between sequential and separate extraction methods, the proportions of these fractions between the two methods was not highly dissimilar (Graph 7). Graphs 10 and 11 show the amounts of copper obtained with each separate extraction step, amongst the triplicate sets of data. Graph 9 shows the results which relate to lower levels of copper (sites T1S1, T1S4, TIS8Sub and TIS8Org., T2S1, T2S2, T2S3 and T2S4). There are a few notable variations between triplicates, particularly sites T1S1 and T2S2 (with variations in organic-bound copper - Step 3), and T2S4 (variations in the reducible copper - Step 2). Overall though, most quantities and proportions of the fractions between triplicate sets appear similar (particularly TIS8Org, and T1S4). Graph 11 shows the triplicate results for copper fractions, for T2S5, the bing and river sediment samples. The triplicate values for all 3 extractions appear to correlate more strongly with one another, with the exception of T2S5, which shows contrasting levels of the oxide and organic-held copper, even though the proportions arc similar. Graph 12 shows the average proportions of the copper fractions in the samples analysed using separate extraction methods. As was seen with the residue copper fraction proportions in sequential extraction, it appears that copper fractions extracted using Steps 1 and 2, vary in direct proportion to one another, at the expense of the organic copper fraction (Step 3). These fractions increase along Transect 2, from T2S1 to T2S5, and are dominant in the subsoil sample (T1S8 Sub.), in sharp contrast to the organic (TIS8Org.) sample. They are also dominant in the bing and river sediment samples.
44
River fraction and XRD results (Graphs 13, 14, 15; Appendices 3a, 3b, 3c, 3d; 5b) None of the graphs in Appendix 3 gave any indication of any of the sulphides within which heavy metals including copper are found in the local geology. Appendix 3a contains the abbreviations used for correlating each peak produced with the mineral that is likely to be present. These are defined below:
As can be deduced from the magnitude of the peaks, quartz and feldspar dominate the mineralogy of the sediment (each constituting over 25%). Muscovite appears to be a minor component (between 5% and 25%), with kaolin, tremolite (a form of amphibole) and chlorite occurring at trace levels (<5%). No evidence points towards the existence of any metal ore bearing sulphides, let alone that of copper. Appendices 3b and 3c are based on a second trial using a portion of the river sediment, in which fragments of what appeared to be pyrite within the sediment were concentrated. These graphs indicate this was not the case, with a very similar pattern to Appendix 3a. The large quartz peak in Appendix 3b (to the right of the tallest peak) was corrected in the analysis used to produce the graph in Appendix 3b. Overall, the river sediment consists mainly of granitic silicate minerals which have persisted under erosion and weathering. Appendix 3d shows the graph produced when a sample of the T2S5 oven-dried soil was analysed. This is similar to those for the river sediment, although some peaks are missing. Quartz and feldspar dominate, with occasional muscovite; chlorite and kaolin peaks are less certain. Graphs 13 and 14 relate to the levels of the total Cu obtained from different particle size fractions in the River sediment. Graph 13 shows the size distribution, which shows mesh size divisions which vary by factors of 2 (except for the 1mm mesh size division). Ignoring the >2mm particle size fraction, it appears that (had a 1mm mesh been used as well) the mass of each fraction is equally distributed. (It is worth noting that a 0.032mm mesh was used, but almost no sediment passed through this.) In general, the river sediment collected is very poorly sorted. Graph 14 shows the copper levels in Ig portions of each size Fraction. Copper levels increase in inverse proportion to the particle size, which could be expected if chalcopyrite or Cucontaining particles are present, with increasing surface area in relation to decreasing particle size.
45
Graph 15 shows this for all of the samples. Overall, the variations in pH appear sustained between pH4.5 and pH5.5, with occasional and slight exceptions. There is no significant contrast between the acidity of natural soils (such as T1S1, T1S10 or T2S1), and those nearby the waste (such as T1S5 or T1S7), or the bing and river sediment samples themselves. The "Building" samples show slightly lower levels, although these are not detrimental. One feature worth mentioning is the progressive decrease in pH from T2S1 towards T2S5, where it suddenly recovers. Overall though, it can be concluded that since copper levels do not relate to pH, the mine waste may not be inducing any significant acid mine drainage.
3.2: Statistical Treatment of Data

Rejection of outliers: Dixon's Q test The Q test was used occasionally during the project, especially as outlying values often occurred in the data presented in this report. The equation used is depicted:
This is applied, whereby the experiment Q value (Qexp) is calculated by dividing the value (xQ -xN) (of the difference between the outlying value and its nearest replicate value), by the spread (the difference between the largest, and smallest value). The Dixon's Q test tables give a critical Q value of 0.970 for a triplicate set (95% confidence). If Q > the critical Q value, the outlier is rejected (Skoog, West and Holler, 1996). There are limits to this method. Inevitably, if 2 of the 3 values are the same, the third value would have to be rejected, as Q would equal 1.000. The test cannot be applied in this situation, and its use may also be dubious, where 2 values are almost identical, although all 3 values are relatively similar (particularly with larger numbers- e.g. 825, 826, 857). Triplicate values which could be viewed with suspicion, may include sets, where, for example, one value is more than double/less than half of the other 2 values. The rejection of outliers was used on one occasion, with some of the pH values obtained for soils T2S1, T2S2, T2S3, T2S4, and the River sediment. Whilst 2 of the replicate data sets agreed almost exactly with one another, the third showed consistently lower values, and further soil samples were analysed as a result, with the new data (in better agreement with the first two sets) being accepted. Although there were other cases where The triplicate values appear dubious (for example, the EDTA-extracted copper values for T2S5 in Graph 5b), the other two results tended to differ from one another, to the extent that the Q values produced did not exceed 0.97. As a result, no other data sets included outliers which were rejected.
46
Correlation and Multiple Regression Statistical methods such as multiple and linear regression are 2 of the many methods which can be used to identify possible relationships between sets of data with the same number of entries. Mathematics of correlation Here is an example of the levels of copper and the other 4 heavy metals being analysed, using the Correlation command on Minitab V13:
For each pair of data sets, 2 values are produced. The Pearson correlation (r) values range from (-1) to (+1), whereby a value of (-1) indicates that the values along the x axis are inversely proportional to those along the y axis; (+1) indicates the opposite trend. In either case, values approaching zero indicate an increasingly unlikely correlation. The r value obtained can be analysed using a t-test, to assess by what percentage the variation within one group, is explained by that of the other group of data:
(r2) gives the decimal equivalent of the percentage value, showing how much (%) of the variation in one group is explained by that in the other group (e.g. for Cu and Mo, r = 0.883, hence r2 = 0,780, and so 78% of the variation in copper levels is determined by those of molybdenum. The p-value (also known as the population correlation coefficient, p) is used to test the significance of the correlation between the 2 groups. The value is inversely proportional to the certainty of a correlation between 2 sets of data; it statistically presents the evidence against it.
47
The relationship between copper and molybdenum is therefore highly significant as p = 0.000. The p value for correlating zinc with nickel is 0.001, and when multiplied by 2 to give the two-tailed R value, the new value (0.002) is considerably less than the 2-tailed value of 0.01. This implies that the correlation is significant at the 1% level (or that there is more than a 99% certainty of this relationship existing) (Mendenhall et al, 1999). Multiple Regression A multiple linear regression is undertaken which takes more than 2 variables into account. This is a flexible model, which is based on the equation given below-
Mendenhall et al (1999) explained the above equation (extract taken from lecture notes):
Although the outcome of this is similar to using correlation as a means of identifying possible relationships, this method and the data produced allows such inter-relationships to be examined more closely. The relationship between 2 variables is considered, in the presence of the other variables. It is never enough to assume that 2 variables correlate with one another, without considering the behaviour of others (as another factor may have caused the 2 variables to behave in that manner). Taking the example of Cu and the other 4 heavy metals again, here is the output by Minitab using the Regression command:
48
The regression equation is based on that seen on page 47, which shows how copper may be determined by all 4 metals. In the next section a list of t and p values are produced. Next, an r2 value is postulated, and from this, a percentage (in this case, 98.2%), which presents the proportion of variation of total copper levels, being determined by the four metals altogether. The ANOVA (Analysis of Variance) reveals the degrees of freedom (DF), the Sum of Squares (SS), Mean of Squares (MS), plus an F and a p value. The F value can be used to determine, how significant the influence of the four metals are on copper, in comparison to any other variations within the model. The F value in the output data is compared to statistical F values. These align with: (1) the regression degrees of freedom (or df1), or the DF value above beside "Regression'' - this is the number of variables (k) (4 metals); and, (2) the degrees of freedom of error (or df2), or Residual Error DF, = (n 1 k). If the experimental F value is greater than the F value in the table, it can be said, that at least one of the variables (the metals) is influencing the levels of total copper. The t values arc compared with those in the table, with (n - 1 - k) degrees of freedom. The p values are treated in the same manner, as with those for correlation. As seen on the previous page, the p value for Mo against Cu is 0.000 (as it was in correlation analysis); however, this time, the p value for Ni against Cu is 0.011. The relationship between Ni and Cu may still be significant at a 95% Confidence level. However, this can be studied further using the t value (= 3.60). With 13 samples, (n 1 k) degrees of freedom equals 9. The t95% value for 9 degrees of freedom equals 3.25, and so the relationship between Cu and Ni is still highly significant. It is interesting to note that Pb also relates to copper, even though this was rejected using correlation alone. Again, copper does not appear to be affected significantly by zinc. The F95% value (against df1 = 4, and df2 = 9) equals 3.63. The experimental value is 79.3, and so the relationship between copper and the metals altogether is highly significant. Trends within the data Copper and other heavy metals Most of this has been discussed in the last section, where copper was found to correlate very closely with molybdenum, and nickel. As 11 of the sites are studied here (and hence n-2 = 9), the t95% value used here is 3.25. Calculations for t are given below:
49
It can be concluded from this alone, that the occurrence of copper at the bings, the river and around Transect 2 appears to correlate linearly with some associated porphyry metals including Mo and Ni. However, Graph 5 showed the relationship between the metals on a logarithmic scale, whereby Pb appear to correlate closely with copper. This has been documented by Nriagu (1979), with the logarithmic relationship between Cu and Zn (zinc often occurs in partnership with lead). With all four metals though, their relationship with copper varies, although, as expected, they associate with copper. Nevertheless, the concentration of Cu is much greater in comparison to the other heavy metals. Plant-available copper, pH and Loss-on-ignition (LOI) It is already known that the proportion of total copper that is plant-available, does not relate to soil pH. However, the actual amount of plant-available copper, along with the plant-available proportion of total copper, pH and LIO were analysed:
Judging by the p values, the only likely relationship may be that between the quantity of plant-available copper, and soil pH. A linear regression graph was produced (Figure 7):
Figure 7: correlation between soil pH, and the Cu extracted using EDTA
50
This shows a very weak linear relationship, with only a 15-20% certainty of it being highly significant. Furthermore, the r value given is 0.438, and so the t value for (23 - 2) degrees of freedom is 0.2232, less than the t95% (df = 21) value of 0.2832. There is more than a 95% certainty that soil pH does not relate to plant-available copper. No correlations amongst total copper, plant-available copper, soil pH or the organic content are found to exist (except between total, and plant-available copper). Relationships with copper fractions (as determined by separate extraction methods) Due to the low number of samples used for sequential extraction, it is inappropriate to apply statistical analysis to these. Having taken into account, the differences between the results relating to separate and sequential extraction, it is still worth investigating the possible relationships with copper fractions, although no definite conclusions are proposed at this stage.
The average values of all 3 copper fractions, plus the relevant loss-on-ignition and plantavailable values were compared. The results reflect the cycle shown on Figure 5; all 3 copper fractions correlate with one another, and also correlate with plant-available copper. P values of 0.000 and 0.001 indicate that these interactions are very apparent. This pattern is further illustrated in Figures 8 through 13, and in Table 5. It therefore appears that the quantity of plant-available copper is determined by all 3 fractions (solution-based, oxide-based and organically combined), although the oxidecombined copper appears to be the most important source.
Table 5: statistical results for comparisons between different copper fractions
51
Figure 8: fractions obtained by extraction steps 1 and 2. Values of Cu i mg/kg oven-dry soil
Figure 9: fractions obtained by extraction steps 2 and 3. Values of Cu i mg/kg oven-dry soil
52
53
Organic Matter The r values produced suggest an inversely proportional relationship between the amounts of each copper fraction and plant-available copper, and organic matter. This is due to the competition between oxide and organic sites. Organic soils strongly retain copper cations, when even the extraction of the "organic" copper fraction is retarded by the presence of
54
organic matter (Ngriau, 1979). However, the p values indicate that this may be uncertain, and t values were calculated (Table 6):
Table 6: correlation between copper fractions
Knowing that t is negative in this case, if positive, those above would fall short of the t95% value (except for LOI and the solution copper fraction). The level of organic matter therefore inhibits the solution copper fraction obtained, but does not affect the oxide-bound or organically-bound copper released. When analysed altogether, the organic copper fraction (Step 3) and oxide-bound copper fraction (Step 2) exert the most influence on plant-available copper levels. Overall, plantavailable copper is strongly influenced by the combination of these 3 variables, with a very high F value (45.36), and an r value of 0.963 (96.3% of the variation explained by these 4 variables):
Finally, it is worth considering how the proportion of these copper fractions affect the availability of copper to plants. The correlation output over-page compares the 3 fractions with the amount of plant-available copper, and loss-on-ignition (over-page):
55
As seen in Graph 12, the proportions of oxide-bound, and organically-bound copper levels share an inverse relationship, which may indicate that each fraction could affect the release of copper from the other. The proportion of solution copper (out of all 3 fractions) also relates strongly to the amount of plant-available copper, and from this, it can be suggested (not concluded) that organic matter in soils at Tomnadashan retains copper, reducing the proportion of extractable copper that is in solution, which subsequently affects that which is available to plants (Figures 14, 15). Both graphs show a correlation which appears to show a proportional relationship, although most values deviate noticeably from either side of the straight line predicted. The lines are also affected by a comparatively high value, and thus a conclusion cannot be reached without further investigation with a much greater population of samples.
Figure 14: loss-on-ignition (%) and solution copper (Step 1 extraction) (mg/kg oven-dry soil)
56
Figure 15: solution copper proportion (% of [Step 1 + Step 2 + Step 3 Cu fractions], and plant-available copper)
3.3: Discussion
Reliability of the data Statistical analysis can only be used with data, which is randomly sampled, which contains the same variance, and which originates from the same population. So, for example, when preparing each triplicate, these should be obtained from the same sample, and should be prepared and treated simultaneously. This was not always the case. The (BCR) separate extraction, Total Cu, and soil pH triplicates were not all performed simultaneously. In both cases, 2 replicates were performed, followed by a third. Although glass beakers containing portions of air-dried samples were used for the BCR extraction soil aliquots (and thereby reducing systematic variability amongst the triplicates), conditions such as temperature (e.g. water bath) may have varied between the 2 preparations. There is also the variability which affects the results produced using the AAS spectrophotometer. When a calibration chart is computed on the machine, even a correlation coefficient of 0.999 may result from a line with each value deviating noticeably on either side of it. Appendix 2, in addition to listing the instruments used, also specifies the precision of the glassware used (pipettes and volumetric flasks). The cleanliness of containers, jars, tubes, etc., also played an important influence on the reliability of the data obtained. The reproducibility of each preparation procedure for each sample is another consideration to be made, particularly with soil pH measurement. Although each group of samples had water added to it, and were shaken quickly, measuring the pH took at least a few minutes,
57
and so the last sample to be measured would have undergone a slightly different procedure to that of the first sample. Heiri et al (1999) described how the positioning of samples for LOI in the furnace affects the degree of combustion, whereby it is more rapid towards the centre. Thu lab book includes the positioning of the samples, which may need to be referenced in any future work. More importantly, the influence of filtration needs to be considered, not just in terms of any excess copper released into the filtrate (which could be partly measured using blanks), but in that the length of lime required, and the type of paper used, could absorb cations. The difference in the time taken for the filtrate lo pass through varies considerably between filter papers 50 and 54. Especially with organic-rich samples, filtration using No.50 Whatman paper could take over 4 hours. This problem was frequently encountered during the sequential and separate extraction experiments. In one scenario, 4 samples had to be left on the bench over the weekend; other samples had been stored in the cool room overnight beneath the fan, where drafts were minimal. Nevertheless, the variation between those samples and the others cannot be ignored. As these samples require refrigerated storage immediately after centrifugation, the influence of temperature will undoubtedly have affected the results (Sahuquillo et al, 1998). Above all, the limited number of samples chosen for the separate extractions, and particularly, the sequential extraction experiments, is too insufficient for any definite conclusions to be drawn on the results obtained. One recommendation is for a full-scale investigation on copper fractions for all 23 samples, using sequential extraction alone, with several replicates. Poor reproducibility of results in sequential extraction methods has been documented by several authors (Balasoiu et al, 2001; Qian et al, 1995; Quevauviller et al, 1997; Rauret, 1997; Sahuquillo et al, 1998; (etc.)). However, the BCR selective extraction scheme is the product of much refinement of sequential methods, with improved uniformity in procedures and results (Kot and Namiesnik, 2000). Total copper levels The levels of copper in soil across Tomnadashan would be considered unacceptable under EC Guidelines. However, the underlying geology, which is enriched with Cu, Pb, Mo, Ni and Zn (Pattrick, 1984), is likely to contribute elevated amounts of these metals into the soil. It is known that soil levels above copper ores may naturally contain Cu levels in hundreds, perhaps thousands of (mg/kg) dry matter. It is also known that associated elements such as Pb and Zn will often correlate with Cu levels, often logarithmically (Nriagu, 1979; Maiz et al, 2000). However, the scope of this is limited to the area around Transect 2 and the bings. The levels and distribution of other heavy metals along Transect 1 may need to be analysed in order to present fully, the distribution of metals at Tomnadashan, and whether it is the case that the whole site is affected by elevated levels. The contrast in copper levels between those along Transect 1 (which passes the bings) and those of the bings themselves indicates that no wind-blown cross-contamination of copper
58
appears to be occurring. The small variations in total copper along the transect do not indicate the presence of any significant mine tailings nearby. However, the elevated levels at T2S5 and at the stream are more suspicious. The analysis of minerals from sites T2S5 and River using XRD, are similar to those occurring in mine tailings at the Aitik copper mine in Sweden (Stromberg and Banwart, 1999), with quartz, feldspar and granitic minerals dominating their thin-actions. Although these are fragments of the underlying bedrock, they are much more dominant in the river sediment, than at the boggy soil sampled at T2S5, which suggests tha; this high input of copper may also be anthropogenic. The partly exposed waste rock seen uphill from these sites could be the source. Stromberg and Banwart (1999) also describe the influence, of the particle size of sediment on the amount of total copper released. Graph 14, which showed the release of copper being inversely proportional to particle size, is in agreement with their findings. The most important trend to note though, is the exponential increase in total copper levels uphill, from T2S1 to T2S5, suggesting that this may be due to a point source of copper which is spreading through the soil downhill. However, as the residual fractions were not analysed for T2S5 or the River samples, it remains to be seen which of them are polluted in terms of phyto-toxicity (copper in polluted soils is more likely to be bound to soil organic matter, oxides and exchange sites, and less in silicates (Rauret, 1997)). Copper levels, as with the other 4 metals, are insignificant along the 3 "Building" sites. The slightly more acidic soil at that area of raised ground (in comparison to soil pH elsewhere) may or may not indicate past industrial activity there. The orange/pale yellow soil, low organic matter and very low moisture content could suggest that these samples reflect historical disturbance of the ground.
Copper fractions The environmental impact or phyto-toxicily of copper cannot be addressed using total copper values alone, even though regulations abide by these (Balasoiu et al, 2001; Gupta, 1996). Tomnadashan is generally vegetated, with long grass and heather covering the site. Nevertheless, it should be borne in mind that selective extractants rarely fulfil that purpose of being selective, and that copper from the "wrong" sites can be released, and can be reabsorbed during extraction (Rauret, t997). The exchangeable, and reducible (oxide-bound) copper fractions may be considered the most labile, und most potentially toxic forms (Balasoiu et al, 2001).
Plant-available copper The generally low proportions of total copper being plant-available, as seen in Graph 6, are characteristic of peaty, upland soils, where copper is known to be strongly retained by accumulating organic matter, and often more so in comparison to other heavy metals (Nriagu, 1979). Furthermore, the ratio of EDTA to the heavy metals extracted, is inversely proportional to the performance of EDTA (Sun et al, 2001), A third consideration to be made, is that in spite of the EDTA solution being set at pH7 (which makes it most efficient at
59
scavenging plant-available fractions) (Cox, 1987), the pH will change during shaking, which will affect the degree of extraction (Hogg et al, 1993). It has been suggested by Qian et al (1995) that plant-available copper is best represented by its exchangeable and organically bound components. As was discussed in the last section, all 3 potentially mobile components of copper correlate closely, both with one another and with plant-available copper. Qian's experiment on sequential extraction showed a strong correlation between the oxide-bound, and organically bound copper, although no other significant correlations v.ere found. However, his study was on agricultural soils, and not upland peat. Other studies have uncovered correlation amongst all fractions (e.g. Maiz et al, 2000). However, he also found that soil pH did not correlate with any copper fraction. Soil pH does not appear to be a direct factor behind copper availability in soils at Tomnadashan. Graphs 9, 10 and 11 showed the levels of all copper fractions extracted. The levels of plantavailable copper are consistently lower than the organically-bound copper, which is in contrast to most findings (Schramel et al, 2000), and which contradicts with Qian's theory of plant-available copper being the sum of both organically, and oxide-bound fractions. Again however, these authors used different soils. EDTA is generally incapable of attacking silicateand oxide-bound copper phases (as well as strongly complexed organic pools), whereas the potency of hydrogen peroxide in releasing substantial quantities of copper in comparison to other extraction methods is recorded (Maiz et al, 2000). In all other examples referenced, the exchangeable copper fraction was generally found to be insignificant, and at least one of the fractions correlated with EDTA-extractable copperAlso, the oxide, and organically-bound copper levels have also been known to share an inversely proportional relationship (Schramel et al, 2000; Quin et al, 1995). Interestingly, the proportion of labile copper (being exchangeable) correlates with plant-available copper; secondly, only the quantity of exchangeable copper correlates with organic matter (LOI). From this, it could be proposed that: (1) readily available (exchangeable) copper is limited in soils at Tomnadashan; (2) all 3 labile" fractions as a whole contribute to plant-available copper, although there are interactions between these phases (there appears to be competition between oxide-held, and organically-held copper sites); (3) the proportion of labile copper being readily available will improve plant availability of the cation; and, (4) the organic content of the soil will inhibit the release of copper, as shown by the inverse correlation between exchangeable copper, and the loss on ignition. In addition, the bing soils are dominated by the residual fraction which is only slowly released (Maiz et al, 2000).
60
One feature to note is the enormity of the copper fractions, in comparison to the levels of total copper. Although the total copper, and copper fraction results originate from different soils, the levels of labile copper in some samples actually exceeds the levels of total copper extracted. Site T1S1 "Sub'' contains total Cu levels of around 200mg/kg (Graph 2), yet the sum of its labile fractions extracted separately occurred at around 250mg/kg (Graph 10). In one of the T2S5 triplicates (Graph 11), the sum of the labile copper fractions amounts to nearly 2000mg/kg, in comparison to the total copper value of 860 mg/kg (Appendix 5c). This stresses the importance of carrying out further investigation, using sequential extraction alone, as separate extractions extract more copper from each phase than expected.
61
4: CONCLUSIONS AND RECOMMENDATIONS

Copper levels in the soil horizon at Tomnadashan are elevated, with natural levels in excess of 100 mg/kg, in breach of EC regulations. However, this is perhaps to be expected as a result of the unique geology of the area. Nevertheless, total copper levels, along with Pb, show much greater concentrations in the bing samples, the river sediment, and at site T2S5. At these sites, copper concentrations range within the 1000s of mg/kg. This, plus the increase in Cu, Pb and Zn uphill along Transect 2 (T2S1 to T2S5) suggest that an influx of copper, possibly from waste, may be affecting the area around Transect 2, and could be contributing to the high levels seen in the river sediment. Mineralogical analysis of the river sediment and particles in the T2S5 sample suggest the presence of copper-binding minerals, which release larger quantities or copper into the environment upon weathering (fining of particle size). Levels of copper and other heavy metals are not very significant along the raised ground where Jefferies' acid plant might have existed. Copper levels along Transect 1 are moderate, undulating, and unaffected by the bings. Soil pH is also restrained within the moderately acidic pH4 to pH6 band, which may suggest that acidification by mine tailings is not a serious issue. Of the total copper present, it is often the case that less than a third is plant-available, and that this may owe to the organic soils which occur naturally, as determined by loss-onignition (between 10% and 20%, except for the bing and river samples). Of the 23 soil samples collected, no relationship between the levels of plant-available copper, total copper, organic matter or soil pH was found, although the proportion of labile copper that is readily exchangeable is known to be retarded by the presence of organic matter. A limited insight into the behaviour of plant-available and semi-mobile copper was gained, although the selective extraction method was modified, and there was a tendency for the levels of labile copper to be exaggerated using separate extraction methods, in comparison to the BCR-approved selective extraction procedure. In general, the quantities of labile copper were much greater at the same sites as those with elevated total copper levels (T2S5, the bings and the river sediment), although it might be suggested that silicate-bound (residual) copper dominates the soils/sediment found at the bings and river sediment. Based upon the separate extraction procedure alone, the proportions of labile copper being oxide-bound, and exchangeable, are both inversely proportional to me proportion which is organically bound. Organic binding persists mainly in less affected soils such as T1S1, T1S4, and its influence decreases uphill along Transect 2, where the presence of oxide-bound copper rises towards T2S5, both proportionally, and in quantity. This may indicate the transport of other metals along with copper downhill, such as Fe and Mn. The slight decrease in soil pH towards T2S5 may also suggest such a process is occurring.
62
Nevertheless, many findings in this report are inconclusive. The selective extraction results are both limited in number, and perhaps misleading (in that seperate extraction may affect both the performance of the extractant (Rauret, 1997), and the sources of copper which are targeted). In spite of some of the good statistical patterns found, further studies need to be performed in order to confirm the correlations. An extensive study of the forms and distribution of copper using all the samples (if possible), with respect to sequential extraction, should be carried out. Particularly for Transect 2, a study on the distribution and speciation of Fe may be useful, which could reveal patterns relating to the increase in oxide-held copper towards T2S5, and the possibility of ore-related minerals such as pyrite dissolving and releasing cations into this area. There is a considerable area between the 2 linear transects which is unaccounted for. According to the 1861 map, this was once characterised by mine waste. It is not known, not even from this report, if this waste may be covered over by vegetation (although the slightly elevated copper levels towards the middle of Transect 1 might give an indication). It could be that infiltration of water out from such material may be contributing to the anomalously high levels of copper along the top of Transect 2. These are only presumptions, which need confirmation in future studies.
63
ACKNOWLEDGEMENTS
First und foremost, I am grateful to Dr. lan Pulford for arranging this project; for coordinating the fieldwork and the sampling; and for providing some of the necessary references needed for the experimental work, and for advising me throughout the term. I am equally grateful to Douglas Turner for his support and advice in the laboratory. I would also like to thank Michael Beglam for his advice and assistance, particularly with the AAS. I thank Drs Flowers, Jarvis and Duncan for contributing their advice to the laboratory work. I also thank the postgraduate students for their assistance in the Research laboratory. I am particularly grateful to Dr. Allan Hall for his advice on identifying the minerals present on the rock samples, and for contributing a few of the samples collected at Tomnadashan. I also thank him for providing the reference journal and the attached maps of the area. My thanks to Dr. Christine Davidson (University of Strathclyde) for providing me with the journal on her results, pertaining to sequential extraction and its reliability.
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84

BSC Dissertation: Environmental Assessment of Soil Quality at The Former Tomnadashan Copper Mine.

Hochgeladen von

Dokumentinformationen

Originaltitel

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

BSC Dissertation: Environmental Assessment of Soil Quality at The Former Tomnadashan Copper Mine.

Hochgeladen von

Copyright:

Verfügbare Formate

1

BSc (Hons) Laboratory dissertation:

ENVIRONMENTAL ASSESSMENT OF SOIL QUALITY AT THE FORMER TOMNADASHAN COPPER MINE

By Malcolm Alexander Sutherland (matriculation no. 9805423)

ABBREVIATIONS SUMMARY 1: INTRODUCTION 2: MATERIALS and METHODS

page 3 page 4 pages 5 - 7 pages 8 - 24

3: RESULTS and DISCUSSION

4: CONCLUSIONS and RECOMMENDATIONS ACKNOWLEDGEMENTS REFERENCES APPENDICES

pages 61, 62 page 63 pages 64, 65 pages 66 - 84

%EDTA BC LOI for BCR

1.2: Mining Activity at Tomnadashan

1.3: Environmental Implications of Mine Waste and Smelters

1.4: Aims and Objectives

2: MATERIALS AND METHODS

Figure 1: entrance to the copper mine, Tomnadashan, near Loch Tay

Figure 4: the soil corer

2.2: Soil Properties and Composition

Properties of oven-dried soil aliquots

2.3: Total Copper Extraction

Table 2: cadmium solutions prepared

2.4: Analysis of Copper Fractions

2.5: The River Sediment

3: RESULTS AND DISCUSSION

3.2: Statistical Treatment of Data

4: CONCLUSIONS AND RECOMMENDATIONS

Das könnte Ihnen auch gefallen