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Title: Spatial and temporal variations in potentially toxic elemental (Sb, Pb, Cu and Zn) and PAH concentrations and associations in run-off from urban and rural areas of Scotland
Author: Macgregor, Kenneth Gordon Neils
ISNI:       0000 0004 6421 1595
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2016
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Since the UK industrial revolution, coal combustion, ore smelting and other industrial activities have resulted in a marked increase in emissions of potentially toxic elements (PTEs) such as antimony (Sb), lead (Pb), arsenic (As), copper (Cu) and zinc (Zn), along with polycyclic aromatic hydrocarbons (PAHs), to the atmosphere. Although stricter environmental regulation and improved technology has led to a notable decline for some contaminant emissions in recent decades, this has not been observed for all elements, e.g. Sb, where only a modest reduction in emissions have been recorded. Once emitted, Sb along with Pb, As, Cu, Zn and PAHs may persist in the environment for considerable periods of time after their release; although their chemical associations may change, elements are not broken down over time and organic contaminants may break down slowly. Above all, PTEs and PAHs are detrimental to human and environmental health, with chemical forms of Sb, Pb, As and PAHs categorised as carcinogenic. Understanding their behaviour and fate in the environment is therefore an important step towards evaluating their likely impact on both ecosystem and human health. Consequently, this study focuses on the release, behaviour and fate of contaminants from current and past anthropogenic sources in the urban and rural environment, with a specific interest in Sb and PAHs, where emissions originate from similar anthropogenic sources, with Pb, As, Cu and Zn also included for comparison purposes. Current and past industrial activity was identified as the dominant source of PTEs and PAHs to the urban environment, with emissions from vehicle, coal combustion and metal smelting identified as main contributors to total contaminant concentrations. Using road dust collected from Edinburgh at five high- and low-traffic roads at a distance of 10 and 50 m from the closest road junction, concentrations of Sb, Pb, Cu, Zn, PAHs and Pb isotope ratios were determined, with road dust undergoing further characterisation using chemical (sequential extraction) and spectroscopic (X-ray diffraction, SEM-EDX) techniques. No consistent trend for the element concentrations released from vehicles braking at 10 and 50 m from the closest road junction was observed. Mean concentrations for Sb, Cu and Zn were 5.3 ± 2.8 mg kg-1, 91.4 ± 48 mg kg-1 and 237 ± 144 mg kg-1, respectively, and were similar to road dust sampled from five high- and five low-traffic locations in Glasgow (Sb 4.5 ± 2.1 mg kg-1; Cu 117 ± 71.9 mg kg-1; Zn: 283 ± 146 mg kg-1). This was in contrast to mean concentrations for Pb and Σ16PAHs obtained from Glasgow (Pb 250 ± 283 mg kg-1, Σ16PAH 7.7 ± 4.3 mg kg-1) where values were approximately double and two-thirds greater than those found in Edinburgh (Pb 135 ± 129 mg kg-1, Σ16PAH 4.7 ± 2.9 mg kg-1), respectively. Lead isotopic analysis of Glasgow road dust (206Pb/207Pb range of 1.140-1.174) showed a strong influence of past emissions from coal combustion and metal smelting, and was in agreement with Glasgow's industrial history. For Edinburgh, the isotopic signature was considerably lower (206Pb/207Pb range of 1.116-1.151), and was influenced moreso by emissions of Australian sourced Pb in leaded fuel. Isotopic signatures in Edinburgh were lowest at easterly locations within 5 km of Edinburgh airport (206Pb/207Pb ~ 1.12), and corresponded with past vehicle emissions from leaded petrol use, and to a lesser degree, emissions from avgas, which was consistent with the mean annual wind direction for Edinburgh. The mobility of elements from the road dust to the aqueous phase were assessed by sequential extraction, and by using road surface water samples which showed mobility decreased in the order of Zn > Cu > Pb > Sb. Road dust characterised by XRD and SEM-EDX had a high proportion of quartz present (~55%), whilst the presence of less abundant minerals such as calcite were found to increase Pb mobility through ease of dissolution into the aqueous phase. For the rural environment, the behaviour and fate of elemental pollution originating from two former mining sites, an Sb mine at Glendinning, SW Scotland, and a Pb mine at Tyndrum in central Scotland was examined. Under specific environmental conditions, Sb was found to be both mobile and immobile in the environment. The chemical weathering of stibnite found in spoil heaps at Glendinning Sb mine demonstrated that ~3% of total Sb can be mobilised during the chemical weathering process, while hydrous Fe oxides and organic matter in the surrounding soil favoured its retention. The retention of Sb, along with Pb, was similarly observed in Loch Tay sediment downstream of Tyndrum Pb mine, where upon deposition, Sb and Pb remained immobile in sediment and allowed the construction of deposition chronologies for two sediment cores to be established. Excellent agreement between the sediment core deposition chronologies was observed, with both chronologies identifying atmospheric deposition as the primary source of Sb to Loch Tay sediment, whilst the dominant source of Pb was from Tyndrum Pb mine ~25 km upstream of Loch Tay. Relative to Sb and Pb, As had the greatest mobility, with its geochemical behaviour and partial retention by the solid phase influenced by the presence of Fe. This was evident in the surrounding soil at Glendinning Sb mine, where As was associated with hydrous Fe oxides present in the solid phase, while at Loch Tay, the redox cycling of Fe resulted in the post-depositional mobility of As in sediment. The use of ombrotrophic peat bogs for this study provided an effective means to assess atmospheric deposition of contaminants over past centuries; they continually accumulate and receive all their nutrients and contaminants exclusively by deposition from the atmosphere. The deposition archives of Sb and Pb from two Scottish peat cores sampled from Great Moss, Cairngorms Mountains, and, Auchencorth Moss, Midlothian, were used to construct chronologies for historic and contemporary emissions, particularly in relation to current and historic anthropogenic activities observed in urban and rural environments. At Great Moss, the deposition of Sb and Pb during the 19th century increased by a factor of 10 and 4, respectively, as a result of the industrial revolution and emissions from the combustion of coal and metal smelting. The trend continued into the 20th century where Sb and Pb deposition peaked ~1950, followed by a decline towards the early 21st century by a factor of 5 and 11, respectively. Over this period of time, the contribution from coal combustion and metal smelting towards total anthropogenic emissions was on the decline, while emissions from the combustion of leaded fuel increased until the ~1980s. Although deposition chronologies before 1970 for Sb and Pb at Auchencorth Moss were generally in agreement with those from Great Moss, several differences were observed after 1970, or more specifically, in the top ~10 cm of the peat core. This was a result of sub-surface perturbations for Ti, Sb, Pb and 210Pb concentrations, and indicated once deposited, elements were susceptible to post-depositional mobility brought about from a change in environmental conditions. The thicker acrotelm layer present at Auchencorth Moss, and the vertical movement of the peat water-table within this layer, resulted in a change in redox conditions and led to the redox cycling of Mn and Fe, which in turn, influenced vertical concentrations of Ti, Sb, Pb and 210Pb. While Sb and Pb are usually found immobile in peat systems, the post-deposition mobility of Sb and Pb at Auchencorth Moss was comparable to a peat core sampled from Flanders Moss, and indicated that under specific environmental conditions, both elements can become mobile in ombrotrophic peat bogs. It is worth bearing in mind however, that these results are the exception, and in all other cases ombrotrophic peat bogs remain a reliable archival material to use.
Supervisor: Graham, Margaret ; Farmer, John Sponsor: Natural Environment Research Council (NERC)
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: antimony ; dust ; contaminants ; anthropogenic activities