NOTTINGHAM TRENT UNIVERSITY

A COMPARISON OF THE HEAVY-METAL LOADING BETWEEN A GRAZED AND UNGRAZED SALTMARSH IN MORECAMBE BAY

by

ANTHONY McKEOWN

Dissertation submitted in partial fulfilment of the BSc (Honours) Degree in Environmental Science

2013

ABSTRACT
Heavy-metals pose a risk to organisms and are substantially more prevalent in the environment as a result of anthropogenic activities. Morecambe Bay, UK is a European Marine site with established estuarine saltmarshes and a history of metalliferous mining in watersheds draining into the bay. The 63m sediment fraction of two separate areas of saltmarsh, grazed and ungrazed, in the Ulverston Channel draining into the north of Morecambe Bay were analysed for their residual fraction of copper, zinc and lead to a depth of 22.86cm by digestion in aqua regia and analysis by inductively-coupled plasma optical emission spectroscopy (ICP-OES). Soil parameters such as pH, Electrical Conductivity (EC), moisture content (%) and organic matter (%) were also determined and with the exception of pH, significant differences between sites were found in all. Despite physicochemical conditions at the ungrazed site seeming more favourable to metal retention, no significant difference in the concentration of any heavy-metal was found between sites and all were below the intervention limits of numerous sediment quality guidelines. The findings suggest that heavy-metal pollution of lower-estuarine saltmarsh in the Ulverston channel is minimal and may be being further diluted by incoming sediment from external non-polluted sources. Further research investigating saltmarshes higher up the estuary with the potential inclusion of sediment fingerprinting techniques could further elucidate the situation.

ACKNOWLEDGMENTS
I would firstly like to thank my tutor and chief supervisor Dr. Nicholas Ray of Nottingham Trent University for his guidance and support throughout not only my project but also the academic years preceding and surrounding it. I would like to also thank, in alphabetical order: Dr. Benjamin Clutterbuck; Dr. Mike Coffey; Dr. Kirsty Mitchell; Nigel Mould; and Sheralyn Smith, all of Nottingham Trent University, for their assistance in the laboratory work and data analysis I undertook. Often these people went above and beyond the call of duty for me and it is very much appreciated. A special thank you must be extended to Neil Forbes, Ranger Supervisor at the National Trust, and Nicola Evans of Natural England, for granting permission to conduct the work on the saltmarshes, which are protected habitats under EU legislation. I must express my gratitude to Will and Victoria Case of Plumpton Cottage Farm, who authorised the sampling of Plumpton Marsh which is owned by their family. A thank you to my friend John-Paul Drake who accompanied me to Cumbria. I must also thank Neil and Lydia Pinder for feeding and watering me during extended stays in Keyworth. Finally, I would like to thank my Mother and Father for their unconditional love and unwavering support for me. I love you both very much.

What would the world be, once bereft Of wet and wilderness? Let them be left, Oh let them be left, wilderness and wet; Long live the weeds and wilderness yet.

From Inversnaid by Gerard Manley Hopkins (184489)

TABLE OF CONTENTS
Abstract .............................................................................................................................................................. 2 Acknowledgments .......................................................................................................................................... 3 1 Introduction ........................................................................................................................................... 10 1.1 Pollution of coastal wetlands ................................................................................................. 10 History of anthropogenic pollution ............................................................................. 11 Contemporary pollution issues..................................................................................... 12

1.1.1 1.1.2 1.2

Heavy-metals ................................................................................................................................ 13 The role of metals in biological functions ................................................................. 13 Metal toxicity........................................................................................................................ 14 Heavy-metal sources ......................................................................................................... 15 Transmission of heavy-metals into the environment .......................................... 18 Heavy-metal behaviour in environmental compartments ................................. 19 Heavy-metals in estuarine systems............................................................................. 22

1.2.1 1.2.2 1.2.3 1.2.4 1.2.5 1.2.6 1.3

Saltmarsh ....................................................................................................................................... 23 Saltmarsh establishment and succession ................................................................. 24 Saltmarsh flora and fauna ............................................................................................... 25 Subsurface hydrology and chemistry ......................................................................... 26 Ecosystem Goods and Services (EG&S) ..................................................................... 27 Protection and restoration ............................................................................................. 28 Saltmarsh loss, current threats and anthropogenic influences ........................ 28 5

1.3.1 1.3.2 1.3.3 1.3.4 1.3.5 1.3.6

1.3.7 1.3.8 1.4

Heavy metals in saltmarsh.............................................................................................. 32 Saltmarsh extent and locations in the UK ................................................................. 36

Aims and objectives ................................................................................................................... 37 Hypotheses ........................................................................................................................... 37

1.4.1

Hypothesis #1 ....................................................................................................................................... 37 Hypothesis #2 ....................................................................................................................................... 38 Hypothesis #3 ....................................................................................................................................... 38 Hypothesis #4 ....................................................................................................................................... 38 1.4.2 1.5 Metal profiles ....................................................................................................................... 38

Morecambe Bay ........................................................................................................................... 38 Geology and geography of Morecambe Bay ............................................................. 39 Metalliferous mining in the area surrounding Morecambe Bay ...................... 41 Background levels of Cu, Zn and Pb ............................................................................ 44 Pollution in Morecambe Bay .......................................................................................... 48 Heavy-metal deposition at Cockley Beck (NY247015)........................................ 49 Saltmarsh in Morecambe Bay ........................................................................................ 50

1.5.1 1.5.2 1.5.3 1.5.4 1.5.5 1.5.6 2

Materials and Methods ...................................................................................................................... 51 2.1 2.2 Description of the Study Area ................................................................................................ 52 Sampling procedure ................................................................................................................... 53 Sampling point generation ............................................................................................. 53 Sampling procedure at each sampling point ........................................................... 54

2.2.1 2.2.2 2.3

Laboratory procedure ............................................................................................................... 55 6

Brackenhurst Campus laboratory (The Bramley Building) ................................................ 55 Clifton Campus laboratory (Rosalind Franklin Building) .................................................... 56 2.4 2.5 2.6 3 Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) ........... 56 Statistical techniques................................................................................................................. 57 Geographical Information Systems (GIS) .......................................................................... 58

Results ...................................................................................................................................................... 59 3.1 Heavy-metals ................................................................................................................................ 59 Plumpton saltmarsh (SD324801) ................................................................................ 60 Plumpton Hall saltmarsh (SD314786) ....................................................................... 61

3.1.1 3.1.2 3.2

Soil parameters ............................................................................................................................ 62 Plumpton saltmarsh (SD324801) ................................................................................ 62

3.2.1

pH ............................................................................................................................................................... 62 Electrical Conductivity ....................................................................................................................... 62 3.2.2 Plumpton Hall saltmarsh (SD314786) ....................................................................... 63

Electrical Conductivity ....................................................................................................................... 64 3.3 Differences ..................................................................................................................................... 65 Heavy-metals ....................................................................................................................... 65 Soil parameters ................................................................................................................... 66

3.3.1 3.3.2 3.4

Correlation analyses .................................................................................................................. 67 Pooled data ........................................................................................................................... 67

3.4.1

Soil parameters..................................................................................................................................... 68 Heavy-metals ......................................................................................................................................... 70 7

3.4.2 3.4.3 3.5

Plumpton Marsh (SD324801) ....................................................................................... 71 Plumpton Hall Marsh (SD314786) .............................................................................. 72

Regression Analysis ................................................................................................................... 72 Pooled data ........................................................................................................................... 72

3.5.1

pH ............................................................................................................................................................... 72 Moisture Content .................................................................................................................................. 73 Organic matter ...................................................................................................................................... 74 3.5.2 Individual .............................................................................................................................. 74

Organic Matter ...................................................................................................................................... 74 3.6 3.7 Multiple regression .................................................................................................................... 75 GIS Interpolation ......................................................................................................................... 75

Inverse Distance Weighting ............................................................................................................. 76 Global Polynomial Interpolation.................................................................................................... 77 Kriging/CoKriging ............................................................................................................................... 78 4 Discussion ............................................................................................................................................... 79 4.1.1 4.1.2 Organic matter .................................................................................................................... 82 Hypotheses ........................................................................................................................... 82

Hypothesis #1 ....................................................................................................................................... 82 Hypothesis #2 ....................................................................................................................................... 83 Hypothesis #3 ....................................................................................................................................... 83 Hypothesis #4 ....................................................................................................................................... 84 4.2 Assumptions ................................................................................................................................. 84 8

4.3 4.4 5 6 7 8 9

Limitations..................................................................................................................................... 85 Improvements to the study ..................................................................................................... 85

Conclusion .............................................................................................................................................. 85 Reference List........................................................................................................................................ 86 Appendix 1: Mines in Cumbria .................................................................................................... 111 Appendix 2: Inventory of Equipment Used ............................................................................ 113 Appendix 3: Raw Primary Data ................................................................................................... 114 9.1 Plumpton Marsh ....................................................................................................................... 114 pH and Electrical Conductivity (Siemens/cm) ................................................. 114 Moisture Content (%) and Loss On Ignition (%) ................................................ 115

9.1.1 9.1.2 9.2

Plumpton Hall............................................................................................................................ 116 pH and Electrical Conductivity (Siemens cm-1) .............................................. 116 Moisture Content (%) and Loss On Ignition (%) ................................................ 118

9.2.1 9.2.2

INTRODUCTION

The pervasiveness of heavy-metals in the environment is of major concern due to their perturbation of biochemical processes, their potential for bioaccumulation in food-webs and the threat they pose to life (van Malderen, Hoornaert & van Grieken 1996). Coastal wetland1 areas such as saltmarsh are depositional environments for suspended organic and particulate matter, which heavy-metals preferentially bind to (Callaway et al. 1998; Spencer, Cundy & Croudace 2003). Those located in or connected to areas with a history of anthropogenic activity can be particularly enriched compared to background levels (Bromberg Gedan, Silliman & Bertness 2009). Saltmarsh extent has been declining worldwide for centuries, primarily due to their location in areas desirable for human settlement (Doody 2008; Weis & Butler 2009). Global mean sea-level (MSL) is predicted to rise over the current century (IPCC 2007a). Any restriction on the ability of saltmarsh communities to migrate or keep pace could lead to further losses and remobilise sediment-bound metals (EA 2007). The loss of a stable sink for these persistent environmental pollutants could increase their availability to connected ecosystems and increase pressures on their healthy function (Morton & Blackmore 2001; Pan & Wang 2012). 1.1 Pollution of coastal wetlands Coastal wetlands are generally typified by saltwater intrusion, low wave energy, low gradients and fine-grained sediments (Orme 1990; Williams (ed.) 1990). Their importance cannot be overstated. Despite occupying less than 9% of Earths land surface, wetlands provide a range of ecosystem goods and services (EG&S) (Costanza et

Wetlands are defined by Article 1.1 of The Convention on Wetlands of International Importance (The Ramsar Convention) as areas of marsh, fen, peatland or water, whether natural or artificial, permanent or temporary, with water that is static or flowing, fresh, brackish or salt, including areas of marine water the depth of which at low tide does not exceed six metres.
1

10

al. 1997; Millennium Ecosystem Assessment, 2005). Wetlands face numerous threats and are suffering a decline in their global extent as a result (Bromberg Gedan, Silliman & Bertness 2009; Silliman, Grosholz & Bertness (eds.) 2009). Although an accurate figure is difficult to identify, the OECD (1996) estimate 50% of global wetlands have been lost since 1900.

Coastlines are dynamic and subject to natural processes which modify them physically, chemically and biologically on varying spatial and temporal scales (Williams, Dodd & Gohn 1991). Due to inadequate knowledge of their nature humans disturb these processes both directly and indirectly, placing multiple, intense and often competing pressures on the coastline and associated habitats (Kay & Alder 2005). Removal or addition of material through dredging and land reclamation are amongst the most conspicuous direct impacts but of equal concern are the insidious effects of various pollutants (Williams (ed.) 1990)(Merrit 1994). The presence of most pollutants in coastal and estuarine systems derive mainly from anthropogenic activities (EA 2007) and with approximately 50% of humans living at or near the coast, the vulnerability of coastal habitats and ecosystems to anthropogenic pollution is significant (Hill 1997). Human utilisation of the coast increased substantially during the last century and with projected coastal populations of over five billion by the end of the current century, pollution and vulnerability are expected to increase (IPCC 2007b). 1.1.1 History of anthropogenic pollution Anthropogenic pollution can be traced back to the initial use of fire (Spengler & Sexton 1983). Burning woody biomass releases heavy-metals (Nriagu 1996; Narodoslawsky, & Obernberger 1996). Sporadic advances in metallurgy drove human societal

11

development through the Iron and Bronze Ages (Photos, 1989) and GRIP2 ice-core analysis indicates that effluents resulting from smelting by the civilizations of ancient Greece, Rome and medieval China were hemispheric rather than localised (Hong et al. 1996). The advent of the Industrial Revolution coupled with an increasing human population led to a substantial rise in resource use and pollution in many guises becoming a more serious, global problem (Candelone et al. 1995; Nriagu 1996; Jrup 2003). 1.1.2 Contemporary pollution issues Heavy-metals are amongst a suite of pollutants of major concern due to their capacity to seriously damage the health of many organisms, ecosystems and habitats (Table 1).
Table 1 Anthropogenic pollutants of chief concern (adapted from Pierzynski et al., (2000)) Compartment Impacted Pollutant Examples Soil Ground Nutrients fertilizers; livestock & pet manure; aquaculture; urban wastewater; urban run-off; septic tanks; fossil fuel combustion Nuclear weapons; nuclear energy installations Fossil fuel combustion; cooking; explosions Surface Eutrophication and contamination of water bodies; Death; mutations; radiation sickness Carcinogenic; mutagenic; teratogenic Contamination of drinking water; ecological risks; human health Human health concerns; ecological risk; Water Air Impacts

Radioactive matter Polycyclic aromatic hydrocarbons (PAH) Pesticides

Insecticides; herbicides; fungicides; etc.

Trace elements

Heavy-metals; elements normally present at low concentrations in soil or plants

Greenland Ice Core Project (GRIP).

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Coastal wetlands are susceptible to almost all of the pollutants highlighted due to their location in or near areas of human development (Merritt 1994). Continuing population growth and the emergence of newly developing nations mean that attempts to remediate these pollutants can struggle to keep pace with their creation. Prediction alone is insufficient to assess their impacts and therefore monitoring of their prevalence and mobility in the environment is essential in understanding their behaviour and minimising detrimental effects (Moriarty 1983). This will increase understanding of their role in fundamental environmental processes and aid the decision-making procedures for remediation and sustainability (Harland, Taylor & Wither 2000). 1.2 Heavy-metals

Heavy-metal is an equivocal term for a class of elements. A lack of consensus on categorisation is clear in literature reviews (Duffus 2002). Criteria used include density and atomic number. Within environmental science, toxicity is the most pertinent attribute but the complexity of elemental speciation and differences in tolerance between organisms renders even this classification problematic. As elements heavymetals cannot decompose and pose a threat for extended periods of time. They are therefore classed as persistent environmental pollutants. 1.2.1 The role of metals in biological functions Metals make up 75% of known elements. As they are not readily ionised metals can endure in ionic form within organisms and thus play roles in biological functions integral to their development and survival (Flora & Pachauri 2010). Iron has long been known as a constituent of haemoglobin but advances in microbiology since the 1970s have elucidated the importance of metals in functions including enzyme catalysis, muscular energy production and protein synthesis (Suckling & Suckling 1980). 13

Certain metals are therefore known biochemically as trace or essential elements and regarded as such when (a) they are present in all living tissues within a zoological family; (b) depletion or removal causes deficiency symptoms which cease when supply is returned; and (c) deficiency symptoms can be ascribed to a distinct biochemical defect (Frstner & Wittman 1981). Certain metals are understood to be vital for optimum human development (Table 2).
Table 2 Essential metals and respective concentrations for human beings (expressed in mg/70kg body weight) (adapted from Frstner & Wittman, 1981, after Vahrenkampf, 1973). Period IA Group IIA VIB VIIB VIII IB IIB

3 4 5

11 Na 70,000 19 K 250,000

12 Mg 40,000 20 Ca 1,700,000 42 Mo 5

25 Mn 30

26 Fe 7,000

27 Co 1

29 Cu 150

30 Zn 3,000

Homeostatic mechanisms within organisms regulate metal concentration fluctuations (Marcheselli et al. 2010). In animals metallothionein proteins containing sulphhydryl ( SH) groups will bind metals such as cadmium and zinc, enabling their excretion (SaugeMerle et al. 2012) (Roosens et al. 2004). Similarly, phytochelatins within plants bind metals into physiologically inert forms (Gusmo et al. 2010) (Zhang, Gao & Qiu 2008). 1.2.2 Metal toxicity Generalising about metal toxicity is difficult due to differences in sensitivity and tolerance across organisms. Fundamentally, protracted exposure surpasses the homeostatic systems ability to handle assimilation and toxicity occurs. Essential elements can thus become harmful in increasing concentrations. Other metals and 14

similar metalloids with no identifiable biological function, known as non-essential elements, can be deleterious even in small quantities. Wood (1974) proposed a classification of elements based on three criteria (Table 3).

Table 3 Classification of elements according to toxicity and availability. Essential elements that can become toxic are highlighted in bold (adapted from Wood, 1974). Noncritical Sodium (Na) Carbon (C) Fluorine (F) Potassium (K) Phosphorous (P) Lithium (Li) Magnesium (Mg) Iron (Fe) Rubidium (Rb) Calcium (Ca) Sulphur (S) Strontium (Sr) Hydrogen (H) Chlorine (Cl) Aluminium (Al) Oxygen (O) Bromine (Br) Silicon (Si) Nitrogen (N) Toxic but very insoluble or very rare Titanium (Ti) Gallium (Ga) Hafnium (Hf) Lanthanum (La) Zircon (Zr) Osmium (Os) Tungsten (W) Rhodium (Rh) Niobium (Nb) Iridium (Ir) Tantalum (Ta) Ruthenium (Ru) Rhenium (Re) Barium (Ba) Very toxic and relatively accessible Beryllium (Be) Arsenic (As) Gold (Au) Cobalt (Co) Selenium (Se) Mercury (Hg) Nickel (Ni) Tellurium (Te) Thallium (Tl) Copper (Cu) Palladium (Pd) Lead (Pb) Zinc (Zn) Silver (Ag) Antimony (Sb) Tin (Sn) Cadmium (Cd) Bismuth (Bi) Platinum (Pt)

Biochemically, toxic effects occur when excessive concentrations cause metals to replace essential ions, compete for sites with metabolites, react with phosphate groups of ADP 3 and ATP4, damage cell membranes and react with SH groups (Alloway & Ayres 1993). 1.2.3 Heavy-metal sources Heavy-metals occur naturally within the lithosphere but comprise less than 1% of earths crust, hence the geochemical term trace elements (Hill 1997). They become isomorphously substituted for macroelements5 within the crystal lattice of primary minerals found in igneous rocks, or sorbed to secondary minerals in sedimentary rocks (Alloway & Ayres 1993). Subsequent chemical and physical weathering followed by

Adenosine diphosphate. Adenosine triphosphate 5 Those elements comprising 99% of Earths crust (oxygen > silicon > aluminium > iron > calcium > sodium > potassium > magnesium).
3 4

15

aeolian and fluvial transportation provides parent material to terrestrial and marine landscapes (Thornton 1981). Hydrolytic weathering mobilises hydronium (H3O+) which can penetrate mineral crystal lattices, create a charge imbalance and break metaloxygen bonds, removing them from rocks in solution. Weaker bonds disassociate more readily. Liberation of lithospheric metals is the primary natural source but others include volcanic eruptions and outgassings (Bagnato et al. 2007), animal excretion (including humans) (Nicholson et al. 2003) and forest fires. Natural sources contribute to the background level of heavy-metals in environmental compartments, which vary spatially according to local geology (Frstner & Wittman 1981; Pierzynski, Sims & Vance 2000; ICMM 2007). Organisms have evolved within background level ranges which are usually low enough not to warrant concern. Occasionally surface or near-surface mineralization results in localized zones of contamination. Organisms may adapt to this (Posthuma & van Straalen 1993) or the area may become reduced in or devoid of life.

Anthropogenic activities have substantially increased both the utilisation of heavymetals and their prevalence in the environment, especially since the Industrial Revolution (Nriagu 1996; Weiss et al. 1999; Jrup 2003). Greenland ice-cores show lead was already one order of magnitude higher than background levels in late 18th century ice due to early civilizations metallurgical abilities (Candelone et al. 1995; Hong et al. 1996). The production and emissions of copper, lead and zinc increased steadily from 1850 and then more rapidly after the post-war economic boom (Nriagu 1996; Jrup 2003) (Figure 1.1).

16

Figure 1.1 Global production and emissions of selected heavy-metals 1850-1990 (Jrup 2003).

Since increased metal consumption is one of the best indicators of material progress (Krech, McNeill & Merchant (eds.) 2004) this general trend is likely to reflect most metals as the surge in resource use has mirrored global population increase. The major activities causing environmental pollution are industrial processing of ores and metals; utilisation of metals and metallic components; and leaching from rubbish and solid waste dumps (Frstner & Wittman 1981). We can distinguish between industrial point sources (such as emissions, effluents and solid wastes from smelters, foundries and mines) and diffuse sources (such as pesticides, insecticides, fertilisers and emissions and material from motor vehicles) (Marcheselli et al. 2010)(Lone, He & Stoffella 2008).
Table 4 Anthropogenic sources of the heavy-metals in this study (adapted from Lone, et al., 2008).

Element Copper (Cu) Zinc (Zn) Lead (Pb)

Sources Electroplating industry, paper industry, fertiliser production, smelting and refining, mining, petroleum refining; biosolids; motor vehicles Electroplating industry, fertilisers; smelting and refining; mining; paper industry; petroleum refining; biosolids; wear & tear Mining and smelting of metalliferous ores; burning of leaded petrol; municipal sewage; fertilisers; petroleum refining; industrial wastes; paints; wear & tear

17

Mining and smelting of metal-bearing ores releases heavy-metals as atmospheric particulates as well as leaching metals into the aqueous phase (Jennings et al. 2008) via acid mine drainage (AMD). The degree of mineralisation of the tailings and surrounding geochemical conditions determine the intensity of metal pollution around mines (Navarro et al. 2008). Dissolved metals resulting from AMD can threaten marine organisms many years after the closure of nearby mines (Grout & Levings 2001) (Johnston et al. 2008).

Since 1990 emissions of many heavy-metals in European countries have reduced significantly due to recognition of their harmful effects and subsequent legislation to lessen their impacts (Travnikov et al. 2012). The ban on leaded petrol in many developed countries has profoundly lowered concentrations found in the environment (Landrigan 2002). 1.2.4 Transmission of heavy-metals into the environment Heavy-metals released as aerosol particles can persist in the atmosphere for varying lengths of time depending on particle size, windspeed, relative humidity of the air and precipitation levels (Alloway & Ayres 1993). The diametric range of heavy-metal aerosol particles is 5nm-20m, though most are 0.1-10m. Gravity causes particles >10m to settle fairly quickly but those <10m can persist in the atmosphere for 10-30 days be transported vast distances from their source, making heavy-metals transboundary pollutants (Steinnes et al. 1997).Airborne particulates return to Earths surface and enter compartments directly by wet or dry deposition. Dry deposition involves gravitational settling, impaction, interception, turbulence, Brownian diffusion and other processes such as turbophoresis and thermophoresis (Shrivastav 2001). Wet deposition

18

occurs when particles are removed from the atmosphere by falling hydrometeors constituting precipitation.

On the ground surface run-off can transport heavy-metals between compartments. Precipitation can leach them into water-tables or wash them from impermeable surfaces into drainage systems. Transport-related substances in particular take this route as they form part of the particulate dust found in urbanised areas (Legret & Pagato 1999) (Turer, Maynard & Sansalone 2001). 1.2.5 Heavy-metal behaviour in environmental compartments The behaviour of heavy-metals in compartments varies according to their speciation and the physicochemical conditions found there, influenced by biotic and abiotic factors (Brown Jr. et al. 1999). pH is the master variable and metal availability generally correlates negatively with it (Calmano, Hong & Frstner 1993; Pierzynski, Sims & Vance 2000; de Matos et al. 2001; Bhargava et al. 2012). As most heavy-metals are cationic they bind readily with anionic constituents. In increasingly acidic conditions, hydrons (H+) occupy or displace metals from anionic sites and increase their availability.

Water Heavy-metals are most toxic and bioavailable as free ions in solution (McLean & Bledsoe 1992) but elevated concentrations in the aqueous phase is rare as solubility is low in neutral and basic waters (Lenntech, 2012). Instead they readily adsorb onto clay and silt particulates which possess high surface areas (Pierzynski, Sims & Vance 2000). These fine particles preferentially bind to heavy-metals rather than sand (Weis & Butler 2009). Whilst some heavy-metals remain sorbed to clay or dissolved organic matter (DOM)

19

(Fest et al. 2008) and humic colloids in suspension the majority eventually settle to become incorporated into sediments.

Soil Soil is a reservoir for heavy-metals and pollution can be long-lasting due to the relatively strong adsorption of metals to organic matter and clay (Alloway & Ayres 1993; Franklin & Jones 1994; Pierzynski, Sims & Vance 2000; Nicholson et al., 2003; Zimmerman & Weindorf, 2010). Clays, especially those containing aluminium, are anionic and able to adsorb hydrated metal cations (Mn+):

Metals are thus held in the soil and prevented from leaching out. They can be released slowly by cation exchange whereby different ions in the soil displace them from the clay surface and into the aqueous phase:

Soil Cation Exchange Capacity (CEC) defines the amount of cations a soil can store. It correlates positively with soil fertility as this property determines the retention of essential elements and their bioavailablity to plants. Clays are good ion exchangers due to their large surface area to volume ratio but their CEC value is much lower than organic matter (Table 5).
Table 5 Cation Exchange Capacity (CEC) of different colloids (Brady, 1990 cited in Mitchell & Everest, 1995)

Colloid Humus (organic) Vermiculite Smectite Fine-grained micas Kaolinite Hydrous oxides

CEC (cmol kg-1) 300 120 90 25 5 3

Non-living organic matter consists of a variety of non-humic and humic compounds with differing properties (Dvok et al. 2003). The former is undecomposed or partially 20

decomposed fragments of plants and soil organisms. The latter is a complex mixture of amorphous and colloidal substances highly-modified from the original organic tissues and containing highly-polymerised compounds (Winfield 1995). Cellulose material broken down to a resistant state of decomposition leaves long protein molecules. Lone electron pairs on the nitrogen atoms of these molecules are donated into empty orbital shells of metal cations to form a ring-like structure known as a chelate. These organomineral complexes restrict the solubility and mobility of metals in soil (Tapia et al. 2010). Complexes with di- and polyvalent metals exhibit the highest stability and stability generally follows the order Cu > Fe = Al > Mn = Co > Zn. Generally, organic matter levels will correlate positively with total metal concentrations in soils (Otte et al. 1993). The influence of organic matter (solid and dissolved) on heavy-metal behaviour is particularly strong in sandy soils such as is found in saltmarshes (Fest et al. 2008).

CEC is tied inextricably with pH. More free H+ ions reduce the available sites for exchange to take place. At higher pH values hydroxyl and carbonate complexes form, reducing metal availability (Keepax, Moyes & Livens n.d.). Humus increases mineral breakdown and nutrient availability (Mitchell & Everest 1995). Humic compounds possess a much higher CEC than clay minerals (Table 6). Organic matter levels can heavily influence the CEC of soils by providing more anionic sites. This creates complexes with heavy-metals, fixing them in the soil and reducing their mobility (Fest et al. 2008).

Solubility and mobility of heavy-metals also depends on characteristics such as redox potential (Eh) and hydrological regime (Issa 2008). Moisture content affects soil solution chemistry and subsequent uptake into the tissue of plants (Misra & Tyler 1999) 21

Typical concentrations of heavy-metals in the soils of England and Wales are presented in Table 6.
Table 6 Typical concentrations (mg kg-1 dry matter) of heavy-metals in the soils of England and Wales (EA, 2010)

Metal Copper Zinc Cadmium Lead

10th Percentile 9 38 0.2 20

Median 18 82 0.7 40

90th Percentile 37 147 1.4 131

Arithmetic mean 23 97 0.8 74

1.2.6 Heavy-metals in estuarine systems Firm evidence exists for the capacity of wetlands to store and accumulate heavy-metals (Valiela & Teal 1974; Windom 1977). Estuaries are open systems linking different environmental compartments and transferring energy and material between ecosystems (Chinery et al. 1979). They receive heavy-metals via the numerous pathways mentioned heretofore. Heavy-metals can be present as free ions and dissolved species but the vast majority become co-precipitated or adsorbed to natural particulates within aquatic systems such as oxyhydroxides, carbonates, sulphides and clay minerals (Calmano, Hong & Frstner 1993; Spencer & MacLeod, 2002). Additionally, many metals form organic complexes with fulvic and humic acids (Kalbitz & Wennrich, 1998)(Tapia et al. 2008). The dynamic conditions and resulting fluctuations in environmental parameters that occur within estuaries makes their processes difficult to analyse and many remain obscure (Balachandran et al. 2005). The mixing of saline and fresh water within estuaries causes abrupt changes in physicochemical conditions (Emmerson , O'Reilly-Wiese & MacLeod 1997; Balachandran et al. 2005) and increasing salinity enhances the deposition of adsorped metals onto flocculated iron oxide and organic particulates (Frstner & Wittman 1981; Bryan & Langston 1992; Balachandran et al. 22

2005; Siddique & Aktar 2012). Most heavy-metals are found bound to sulphides in the anoxic zone (Weis & Weis 2004). Changes in physicochemical conditions such as an increase in soil acidity or a reduction in organic matter can mobilise metals in the residual fraction (Vega et al. 2009). Numerous sediment quality guidelines (SQGs) have been devised worldwide and the values for Cu, Zn & Pb in some of the most popularly cited are presented in Table 7 & 8.
Table 7 Sediment Quality Guidelines of various countries and respective concentrations.

Cu Zn Pb References LEL 16 120 31 Ontario Guidelines Fletcher et al. (2008) SEL 110 820 250 ISQV-Low 65 200 75 Hong Kong ISQVs (Bai et al. 2012) ISQV-High 270 410 218 Class I 35 150 60 Sediment Quality Criteria of China (Bai et al. 2012) Class II 100 350 130 LEL: lowest effect level; SEL: severe effect level; ISQV: interim sediment quality value.
Table 8 Screening Quick Reference Table (SQuiRT) for heavy-metal concentrations in marine sediment mg kg-1 (Buchman 2008)

Guidelines

Trace Element

Threshold Effects Level (TEL) 18.7 124 30.2

Effect Range Low (ERL) 34.0 150 46.7

Probable Effects Level (PEL) 108 271 112

Effects Range Median (ERM) 270 410 218

Apparent Effects Threshold (AET) 390(Microtox & Oyster Larvae) 410 (Infaunal community) 400 (bivalve)

Cu Zn Pb

1.3

Saltmarsh

Saltmarshes are communities of grasses, low shrubs and herbs which form in the intertidal zone of low-energy coastal regions within the temperate to mid-latitudes (Allen & Pye 1992). Their defining feature is the varying periodic submergence by saline waters that they experience due to their position at the transitional zone between land and sea (Adam 1990). This location creates the dynamic conditions which make saltmarshes amongst Earths most fertile and biologically productive coastal habitats (Bromberg Gedan, Silliman & Bertness 2009). Saltmarshes had traditionally been considered as wastelands (Boorman 2003) and claimed for various purposes, resulting 23

in a steady decline worldwide but recent recognition of the many EG&S they provide has led to a reappraisal of their worth and subsequent protection under EU legislation6 (Costanza et al. 1997; English Nature 2000; Jones et al. 2011). Despite a long history of study (Chapman, 1939; Chapman, 1940) debate still surrounds many of the processes governing saltmarsh establishment, development and ecology which has implications for the decision-making processes of management plans aimed at protecting and restoring this precious habitat. 1.3.1 Saltmarsh establishment and succession Saltmarsh formation varies between locations but is generally regulated by four physical factors: tidal regime, sediment supply, wind-wave climate and relative sea-level fluctuations (JNCC, 2004; Jones et al. 2010). Essentially, in sheltered conditions fine sediments suspended within tidal waters settle onto a variety of substrates and subsequently become colonized by highly-adapted terrestrial angiosperms (Quigley & Crump 1986; Packham & Willis 1997). Saltmarsh can thus be seen as a highly-modified terrestrial ecosystem (Adam, 1990). Initial colonisation by vascular plants requires a stable substrate for root systems. Mucilage7 excreted by microalgae, particularly epipelic diatoms (Coles 1979), is assumed to aid sediment stabilization by binding particles together and increasing the critical shear stress required to initiate erosion (Tait, Lane & Carr 1988; Underwood 1997) (Smith & Underwood 1998). Pioneer species must be specially adapted to tolerate the harsh conditions associated with tidal submergence (EA, 2007). Known as

Various forms of saltmarsh are afforded protection under the EU Council Directive 92/43/EEC of 21 May 1992 on the conservation of natural habitats and of wild fauna and flora, commonly known as the Habitats Directive. 7 More precisely known as extracellular polymeric substances (EPS).
6

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halophytes8 they are classed as salt-accumulators, salt-includers or salt-excluders (Shelef et al. 2012). These adaptations are not exclusive to halophytes but are characteristic features that have evolved in them (Manousaki & Kalogerakis 2011). Once established, pioneer vegetation traps and inhibits the re-suspension of incoming sediment, stabilising it further and adding organic matter upon death. Marsh elevation gradually rises and the developing soil stays drier for longer, allowing other lesstolerant species to colonise (Boorman 2003). Adequate sediment supply, protection from erosive wave-action and stable or gradual sea-level fluctuations enable its continual growth. Four types of saltmarsh are generally recognized: pioneer marsh, low marsh, upper or high marsh and transitional or driftline marsh (EA, 2007). A distinct vegetation zonation from mean low-water (MLW) to mean high-water (MHW) is usually apparent but different successional stages occur depending on a variety of factors at each site. Often creeks will form in response to ebb tides, freshwater flow from the land or changes in geomorphology over time (Gray 1972). Terraces can form at different levels separated by the creeks and often these will support different communities according to their tolerance to salinity (Quigley & Crump 1986). 1.3.2 Saltmarsh flora and fauna The harsh conditions within saltmarshes limits species diversity but the abundance of those present can be high (Adam 1990). Net primary productivity (NPP) of saltmarshes is relatively high compared to other ecosystems, ranging between 2-4 kg above-ground dry matter/m2/year (Valiela, 1975; Broome & Craft, 2000; Barnhisel, Darmody & Daniels (eds.) 2000). High percentages of this are exported away from the marsh to the

Plants tolerant of saline conditions, from halo- meaning salt and phyte meaning plant.

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littoral zone and beyond where it provides food for microorganisms and detritivores and forms the basis of food-webs important to humans (Valiela, 1975; Odum 1988). Spartina anglica is a particularly well adapted halophyte. It has deeply recessed respiratory pores to reduce water loss and glands to secrete salt as well as thick, leathery leaves which protect against tidal scour by water-borne silt. It also has an elaborate root system. Fine surface roots bind the mud and long thick roots with air channels hold it firmly within it (Colebourn 1984). Fauna diversity in saltmarshes is also low and the most ubiquitous animal found is birds (Packham & Willis 1997). Other animal visitors may include mink, water voles and other rodents from the land as well as aquatic creatures such as seals and dolphins at high tide (Adam 1990). 1.3.3 Subsurface hydrology and chemistry The chemistry of saltmarsh is complex and varies between sites but a number of general characteristics can be described. Due to waterlogged conditions soil sediments are predominantly anaerobic and exhibit reducing conditions (Seliskar & Gallagher 1983) (Adam 1990). Dissolved sulphur in seawater is approximately three times the order of magnitude found in freshwater and sulphur reduction is therefore an important anaerobic decomposition process within saltmarsh (Odum 1988) (Table 10). Sulphur is present primarily as sulphide (S2-) and sulphate SO42. Oxygen can be introduced to the rhizosphere by plants and modify the conditions in the subsoil (Beeftink & Nieuwenhuize 1986) (Weis & Weis 2004). Saltmarshes do not typically suffer from nutrient deficiencies (Packham & Willis 1997) but nitrogen is often the limiting factor for plant production in some marshes (Jefferies & Perkins 1977; Kiehl, Esselink & Bakker 1997). Plants utilise nitrogen in the inorganic forms of nitrate (NO3 -), nitrite (NO2 -) and ammonium (NH4 +) which enter saltmarshes primarily bound to clay

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materials within inundating waters (Weis & Butler 2009). The rate of clay accretion can thus affect the rate of vegetation succession (van Wijnen & Bakker 1997).
Table 9 Comparison of physical characteristics between tidal freshwater marshes and salt marshes (adapted from Odum, 1988).

Tidal freshwater marsh Location Geographical distribution Salinity Tidal range Head of the estuary (above the oligohaline zone) Worldwide, usually associated with rivers Annual average below 0.5 ppt Ocean-derived lunar tide, often greater amplitude than nearby salt marshes Silt-clay, high organic content, lowmoderate root and peat content Low gradient, little undercutting Low sinuosity Trace (approximately 1 ppm) Moderate to strongly reducing (multiple redox pairs) Rare or absent High concentrations

Saltmarsh Mid and lower estuary Worldwide, not always associated with rivers Annual average 18.0 - 35.0 ppt Ocean-derived lunar tide

Sediments Streambank morphology Stream channel Dissolved sulphur Sediment redox potential Reduced iron-sulphur compounds Dissolved and particulate organic carbon

More sand, lower organic content, higher peat and root content Steeper gradient, more undercutting Moderate to high sinuosity Very high (approximately 2500 ppm) Strongly reducing (sulphur redox pairs most important) Plentiful Moderate to low concentrations

1.3.4 Ecosystem Goods and Services (EG&S) EG&S are the benefits humans derive from natural processes (Millenium Ecosystem Assessment, 2005; Jones et al., 2011). Saltmarshes supply multiple EG&S. Their topography and vegetation act as critical nurseries for marine and estuarine species, provisioning coastal fisheries that account for 90% of fish catch worldwide (UNEP, 2006; Silliman, Grosholz & Bertness (eds.) 2009). Refuge from predation is suggested as their main attraction rather than detrital food provision (Boesch & Turner 1984). Their position on riverbanks and coastlines acts as a buffer between land and sea, providing a 27

natural sea-defence (Cooper et al. 2001) as their vegetation binds soils and attenuates waves, protecting against shoreline erosion resulting from storms and rising sea-levels (Bromberg Gedan, Silliman & Bertness 2009). Saltmarshes filter excess nutrients deriving from upland areas, particularly nitrogen from agricultural run-off, mitigating eutrophication effects in adjacent coastal ecosystems (Deegan et al., 2012). Carbon sequestration is favourable as the high NPP locks carbon in organic matter which is subsequently incorporated into the marsh by lithogenic processes (Jones et al. 2011). Similarly, saltmarshes can act as a sink for multiple pollutants in solution or adsorbed onto incoming sediment (Beeftink & Nieuwenhuize 1986). 1.3.5 Protection and restoration Recognition of its value has led to a reappraisal of saltmarsh and subsequent protection under the EU Habitats Directive. The UKs obligation to restore habitats has seen many areas of saltmarsh incorporated into Biodiversity Action Plans (BAP) nationwide (JNCC, 2012). Managed Realignment (MR) has been conducted in many areas of south-east England. This involves allowing the sea to breach defences which are normally maintained with the rationale that intertidal habitats will establish and this will support flood defence and improve ecological conditions (Burd 1995). 1.3.6 Saltmarsh loss, current threats and anthropogenic influences Saltmarshes are amongst the most anthropogenically impacted marine ecosystems and few in the developed world are unaffected by human activities (Doody, 2008; Silliman, Grosholz & Bertness (eds.) 2009). Kennish (2001) suggests tidal saltmarsh losses of over 50% in the USA due to physical modifications, which alongside chemical impacts are the most conspicuous and prominent. The high NPP and relatively flat topography of saltmarshes facilitates their enclosure and drainage for agriculture and livestock grazing 28

(Silliman, Grosholz & Bertness (eds.) 2009). Attempts to control mosquito populations led to the infilling of creeks and pans as well as the use of pesticides on many saltmarshes in the USA (Bromberg Gedan, Silliman & Bertness 2009) (Weis & Butler 2009). In south-east England saltmarshes have been declining continuously at a rate of approximately 40 ha a-1 for the past 50 years (Hughes & Paramor 2004).
Table 10 Recent saltmarsh loss at sites in south-east England (adapted from French and Burningham, 2003)

Location Orwell estuary (Suffolk) Stour Estuary (Suffolk/Essex) Hamford Water (Essex) Blackwater estuary (Essex) Dengie (Essex open coast) Crouch estuary (Essex)

Net saltmarsh loss in hectares and (%) 1973-98 46 ha (46%) 157 ha (59%) 255 ha (29%) 197 ha (22%) 64 ha (14%) 159 ha (34%)

The reasons are largely unknown and research can be complicated by a number of factors. Isostatic rebound is thought to be exacerbating rising MSL by causing a relative sea-level (RSL) rise (Jones et al. 2011) at a rate above which saltmarsh can keep pace (Doody 2004)(Figure 1.2).

Figure 1.2 Rates of isostatic rebound in cm a-1 across the United Kingdom & ire (Jones, et al., 2011)

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Areas in the south-east are subsiding and this may be contributing to pressure on the saltmarsh communities. Some in areas of neutral or positive uplift such as Morecambe Bay are actively accreting (Joint Nature Conservation Committee (JNCC) 2004) Studies suggest saltmarsh can keep pace with rising sea-levels. French & Burningham (2003) used Sedimentation-Erosion Tables to deduce that vertical sedimentation over 5 and 40 year timescales easily outpaces a post-1964 sea-level rise of 2.4 mm a-1 (Table 11).
Table 11 Indicative vertical sedimentation rates at sites in Southeast England (adapted from French and Burningham (2003))

Location Orwell estuary (Suffolk) Blackwater estuary (Essex) Dengie (Essex open coast)

Saltmarsh sedimentation (mm a-1) 6 3.3 to 7.1 5 to 11

Measurement Period & Source 1997-2001; CERU (unpublished) 1995-1998; Cahoon et al. (2000) 1985-1988; Reed (1988)

Rotman et al. (2008) used sediment fingerprinting to interpret the processes involved in sediment transportation. Using environmental magnetism to determine and quantify sediment provenance, which is not possible using SETs, they were the first to adopt the technique at a MR site. Relatively few possible sediment sources made the site ideal. Analysing material found at proximal sources revealed that the majority of new accretions (54%) originated from established saltmarsh immediately seaward of the reclamation. Erosion was observed in the creek network and with the study having been undertaken just four years after breaching, it was suggested this may reflect an adjustment to the new hydrological processes. If so, other sources will need to contribute more material otherwise accretion may decline, as has been observed at other MR sites. If not, it has profound implications for further schemes and the legal obligations requiring no net-loss of habitat. Refined use of this technique would include a consideration of distal sediment sources within the broader estuarine system. 30

Coastal squeeze describes the inability of saltmarsh to migrate landward due to physical barriers. It has been blamed for saltmarsh loss in areas where land is protected by seawalls. Provided they receive a sufficient supply of sediment saltmarsh can extend seaward and thus the claim that coastal squeeze is primarily to blame for losses in these areas is refuted by some researchers. Invertebrate infauna is suggested to impede plant colonisation through bioturbation, herbivory and seed consumption (Hughes & Paramor 2004). Conversely, Morris et al. (2004) assert that the presence of such infauna is essential for healthy mudflat ecology with bioturbation providing adequate oxygenation for other organisms which in turn provide sustenance for indigenous and migratory birds.

Saltmarshes vulnerability to pollution stems from their location in or near estuaries and coastlines and the various inputs to these areas from coastal waters, local run-off, riverine constituents and atmospheric deposition (Callaway et al. 1998). Agricultural run-off of manure, fertilisers and herbicides can introduce new compounds and alter nutrient budgets. Mason et al. (2003) studied the effect of herbicides on microalgal assemblages in field trials and controlled laboratory conditions. They concluded that sublethal concentrations similar to those found in British saltmarshes could contribute to erosion by reducing both the growth of epipelic diatoms and their photosynthetic efficiency, affecting sediment stabilization. Nutrient enrichment can reduce subsurface biomass and increase microbial decomposition, affecting geomorphology by destabilizing creek-banks which subsequently convert to unvegetated mudflats (Deegan et al. 2012).

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In Europe, grazing by livestock is one of the oldest traditions and this has a major effect on the ecology and geomorphology of the saltmarshes (Jensen, 1985; Silliman, Grosholz & Bertness (eds.) 2009). Six main impacts arise from grazing: defoliation of plants; removal of plant material; treading and pawing deposition of faeces; deposition of urine; and uprooting plants, which are growing in soft sediments (Jensen et al. 1985). In ungrazed areas natural succession dictates the changes in vegetational communities (Bos et al. 2005). Reimold et al. (1975) found aerial plant production and fiddler crab numbers to be reduced in a grazed saltmarsh community compared to ungrazed and formerly grazed areas, suggesting that the lower biomass production has an effect on detritivore populations. Abandoning grazing in an area can result in a loss of biodiversity but both biomass and litter production can increase due to the vigour of the domineering species (Bos et al. 2005; Silliman, Grosholz & Bertness (eds.) 2009). 1.3.7 Heavy metals in saltmarsh Heavy-metals enter saltmarshes in aqueous form or bound to the suspended particulates essential to their development (Beeftink & Nieuwenhuize 1986). Their deposition and subsequent incorporation by lithogenic processes effectively remove them from circulation and reduce their bioavailability (EA, 2007). Saltmarshes are therefore considered sinks for heavy-metals (Doyle & Otte 1997). Incorporation into saltmarsh is affected by the hydrological regime and physicochemical conditions (Suntornvongsagul et al. 2007; Reboreda & Caador 2007). Upon arrival in the saltmarsh, heavy-metals become distributed between the sediment, porewater and within plants (Weis & Weis 2004). Most are found as sulphate precipitates or complexed with organic matter in the porewater (Giblin et al. 1980). Saltmarsh plants are generally tolerant of heavy-metals (Valiela & Teal 1974; Windom 1977; Suntornvongsagul et al. 2007). Many accumulate heavy-metals in aerial and subsoil organs (Duarte et al. 2010) 32

and the capacity of species such as Phragmites australis for the phytoremediation of contaminated areas has been recognized by several studies (Weis & Weis 2004; Windom et al. 2001). The potential for heavy-metal translocation via uptake and release by plants or erosion and remobilisation of contaminated sediments is of more concern than any effects on the plants themselves (Burd 1995).

Emmerson et al. (1997) used multivariate statistical techniques to assess the spatial distribution of heavy-metals at various locations in the Blackwater Estuary, Essex. A general seaward decrease in heavy-metal concentrations was found, suggesting that heavy-metals derived from local anthropogenic sources higher up the estuary. Elevated levels were found in one lower estuary location which was not comparable with a site a similar distance from the nearest urban area. The former area is an enhanced depositional environment with extensive mudflats and saltmarshes. Where dilution and dispersion of discharges does not occur, these conditions may promote rapid incorporation of pollutants into sedimentary landforms and such factors can be taken into account when designing regeneration schemes. Landward to seaward decrease of metal concentrations in estuarine sediment has been documented in previous studies(Mller & Frstner, 1975). As well as the solubilisation of metals due to saline and freshwater mixing, fluvial sediments enhanced with heavy-metals can be diluted by marine sediments originating from unpolluted sources (Mller & Frstner, 1975).

Otero & Macias (2002) looked at the parameters of soil interstitial water and its effects on heavy-metal concentrations in saltmarshes of Northern Spain. They found spatial and seasonal variations in all variables which could be attributed to redox cycles of Fe and S. Soils sparsely colonised by vegetation had a higher pH and lower concentrations of 33

heavy-metals in summer. The opposite was found for soils densely colonised by S. maritima, which showed a decrease in pH and concomitant increase in heavy-metal concentrations. This was attributed to an increase in soil aeration and subsequent oxidation of metal sulphides such as Acid Volatile Sulphate (AVS) and pyrite. Burke et al. (2000) compared the release of metals by two saltmarsh grasses in field and laboratory conditions. They found that Spartina alterniflora both accumulated and released significantly more metals than Phragmites australis. This could have repercussions for restoration schemes within contaminated areas, with S.alterniflora possibly liberating sediment-bound heavy-metals and making them available to detritivores and food-webs surrounding them. Salinity can also affect the accumulation of metals in vegetation and a positive correlation has been shown to exist between salinity and translocation to the shoots of certain saltmarsh plants. Fitzgerald et al. (2003) suggest the inclusion of such considerations when choosing species for biomonitoring purposes. MacLeod et al. (1999) studied the effects of a MR scheme on metal and nutrient loading of sediment. Analysing two fields pre- and post-inundation, increased concentrations of lead, chromium and copper were found, confirming expectations that the sediments would become a sink for heavy-metals. Duarte et al. (2010) looked at underground processes and the heavy-metal concentrations in leaf, stem and root tissues of saltmarsh plant species of the Tagus estuary, Portugal. The highest concentrations were found in the plant root systems, suggesting the belowground biomass and sediment represent the major pools of heavy-metals in these saltmarshes with cycling between the two effectively acting as a sink.

Investigating the distribution of trace metals in sediments of the Mersey estuary over two decades, Harland et al. (2000) deduced that a significant rise in mercury levels 34

between 1989-1992 could be attributed to the erosion and subsequent redistribution of saltmarsh sediment within the monitoring area. Their hypothesis was supported by a subsequent reduction in levels which paralleled the abatement of saltmarsh erosion by the mid-1990s. The concentrations of heavy-metals found in saltmarsh sediments depends on a number of factors and shows the wide range found worldwide (Table 12).
Table 12 Average Cu, Zn and Pb concentrations (g g-1) in bulk sediments of saltmarshes around the world

Marsh Site (Location)

(New York)

Cu
12-600 6-150 26.3 23-52 27.6 89.1 67.2 45.79

Zn
25-500 19-225 107.1 61-202 167.6 427.4 320.6 105.0

Pb
25-700 12-200 36.1 20-126 65.2 126.9 199.3 26.7

Reference
Cochran, et al. (1979, cited in (Weis, Callaway & Gersberg 2001)) Bricker et al. (1993 Weis, et al. (2001)

Rhode Island Oneonta Slough (Tijuana Estuary, USA) (Medway Estuary Kent, UK) Hortas (Tagus Estuary, Portugal) S. Joo da Talha (Tagus Estuary, Portugal) Rosrio (Tagus Estuary, Portugal) Karnafully River Coast

(Spencer & MacLeod 2002) Frana, et al. (2005) Frana, et al. (2005)

Frana, et al. (2005) (Siddique & Aktar 2012)

Table 13 Average Cu, Zn and Pb concentrations (g g-1) in bulk sediments in UK saltmarshes Marsh Site Humber Mersey Solway Rother Medway estuary Two Tree Island Salcott South Woodham Tollesbury Walton Cu 54 84 7 11 23-52 35 22 27 17 23 Zn 252 379 59 46 61-202 104 112 130 83 71 Pb 113 124 25 20 20-126 85 30 32 36 39 Reference (Bryan & Langston 1992) (Bryan & Langston 1992) (Bryan & Langston 1992) (Bryan & Langston 1992) (Spencer & MacLeod 2002) (Fletcher et al. 1994) (Fletcher et al. 1994) (Fletcher et al. 1994) (Fletcher et al. 1994) (Fletcher et al. 1994)

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Little Oakley Dengie

20 20

108 77

55 36

(O'Reilly Wiese, Bubb & Lester 1995) (O'Reilly Wiese, Bubb & Lester 1995)

Although heavy-metals can be fixed in saltmarsh sediments for extended time periods, a change in conditions could cause established saltmarshes to erode and remobilise sediments-bound metals back into the environment (EA 2007). 1.3.8 Saltmarsh extent and locations in the UK Saltmarsh in the UK is widely distributed (EA, 2007). Of the 34,000 hectares in England (Phelan, Shaw & Baylis 2011) the vast majority are found within five predominantly estuarine areas (Figure 1.3).

Figure 1.3 Distributions and approximate extent of saltmarsh in the UK, by county based on JNCC data circa 1990. Note: figures (ha and km) are based on 1:50,000 maps and are meant to facilitate comparisons. Field surveys since they were drawn up have greatly increased our knowledge of the resource which is bigger than indicated by the figures. Source: all maps provided by J.P. Doody; Coastal Lagoons map includes data from Barne et al. (19951998). (Adapted from Jones et al. 2011).

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1.4 Aims and objectives The aims of this study were to: ascertain the magnitude and horizontal spatial distribution of copper, zinc and lead in the sediment of two estuarine saltmarshes within the Morecambe Bay European Marine Site; compare the concentrations of copper, zinc and lead and physicochemical conditions between a grazed and ungrazed site; investigate whether they act as a sink for heavy-metals deriving from contemporary and historic pollution sources in the area.

Although extensive literature relating to heavy-metals in saltmarshes exists, no papers could be found pertaining to the differences in their loadings between grazed and ungrazed sites. A gap in the knowledge therefore exists which forms the foundation of the study. It is expected that higher levels of organic matter will be present in the ungrazed saltmarsh and that this will increase the retention of heavy-metals. 1.4.1 Hypotheses Each saltmarsh represents a sampling site chosen for their specific characteristics. Both are estuarine marshes located in the Ulverston Channel. They differ in size, Plumpton being over three times larger at 32.5 ha compared to Plumpton at 7.5 ha. The saltmarshes are separated by a railway viaduct spanning the low-estuary. Distinctively and most importantly, Plumpton Hall is a rare example of an ungrazed saltmarsh in Morecambe Bay whereas Plumpton saltmarsh is intensively grazed by sheep. Hypothesis #1
H0 The average concentrations of all heavy-metals at Plumpton Hall will not be significantly higher than at Plumpton.

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H1 The average concentrations of all heavy-metals at Plumpton Hall will be significantly higher than at Plumpton.

Hypothesis #2
H0 Organic matter levels at Plumpton Hall will not be significantly higher than at Plumpton. H1 Organic matter levels at Plumpton Hall will be significantly higher than at Plumpton.

Hypothesis #3
H0 There will not be a significant positive relationship between organic matter and all heavy-metals. H1 There will be a significant positive relationship between organic matter and all heavy-metals.

Hypothesis #4
H0 There will not be a significant negative relationship between pH and all heavy-metals. H1 There will be a significant negative correlation between pH and all heavy-metals.

1.4.2 Metal profiles Three heavy-metals were the focus of this study: copper, zinc and lead. All have known potential for harmful effects on organisms in elevated concentrations (Hogan 2011; Meena et al. 2005)(Table 14)
Table 14 A summary of the fundamental chemical attributes of the heavy-metals of pertinence to the study

Element (Symbol) Copper (Cu) Zinc (Zn) Lead (Pb)

Atomic Number 29 30 82

Atomic Mass 63.546 0.003 u 65.38 0.002 u 207.2 0.1 u

Group IB IIB IVA

Electron Configuration [Ar] 3d [Ar] 3d [Xe] 4f

14 10

Concentration in oceanic water ~ 0.1 g l < 1 g l

2 -1

4s 4s

10

-1

5d

10

6s 6p

0.001 0.014 g l

-1

1.5 Morecambe Bay Morecambe Bay (54.1167 N, 3.0000 W) straddles the border between Cumbria and Lancashire in north-west England and covers an area of 310km2 (Figure 1.4).

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Figure 1.4 The location of Morecambe Bay on the north-western coastline of England. Note: the landmasses of Eire and Northern Ireland have been omitted. Created using ESRI ArcMap 10.0.

The confluence of five rivers draining into the bay coupled with a macrotidal regime creates the largest continuous area of sandflats and mudflats in the UK, representing approximately 12% of the UKs intertidal area (Annan 2001; Oceana 2012). These conditions provide habitat for a plethora of organisms, both resident and migratory, leading to the area being chosen as a European Marine Site (EMS) amongst other designations (Table 15).
Table 15 Special designations and their spatial extent within Morecambe Bay (Natural England, 2012).

Designation Special Area of Conservation Special Protection Area Site of Special Scientific Interest Area of Outstanding Natural Beauty

Description Designated under the EUs Habitats Directive Designated under the EUs Birds Directive Designated under the Wildlife and Countryside Act 1981 (as amended) Designated under the National Parks and Access to the Countryside Act of 1949

Area (ha) 61506.22 37404.60 25665.23 7500.00

1.5.1 Geology and geography of Morecambe Bay The geology of the Morecambe Bay area is extremely varied (Figures 1.5-1.7)

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Figure 1.5 Bedrock geology of the Morecambe Bay area with the catchment areas in South Cumbria draining into the Ulverston Channel overlaid. Created using ESRI ArcMap 10.0. Data sources: (1) BGS Bedrock Geology 1:625k Contains Ordnance Survey data Crown copyright and database right 2013.

Much of the geography of Morecambe Bay is a result of its superficial geology, which consists of material deposited by glaciers during the last ice age (Figure 1.6).

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Figure 1.6 Superficial geology of the Morecambe Bay area with the catchment areas in South Cumbria draining into the Ulverston Channel overlaid. Created using ESRI ArcMap 10.0. Data sources: (1) BGS Superficial Geology 1:625k Contains Ordnance Survey data Crown copyright and database right 2013.

Although solid rock outcrops are present, the coastline is comprised mainly of unconsolidated sediments of Quaternary age which can be up to 80m thick (Tooley 1987). 1.5.2 Metalliferous mining in the area surrounding Morecambe Bay Many economically important minerals have been exploited during a long history of mining in Cumbria and ores are widely distributed (Appendix 1: Mines in Cumbria). 41

Figure 1.7 Combined bedrock and superficial geology of the Morecambe Bay area. The locations of old mines and the catchment areas in South Cumbria draining into the Ulverston Channel have been overlaid. Key has been omitted but is a combination from Figures X and X. Created using ESRI ArcMap 10.0. Data source: BGS Bedrock and Superficial Geology 1:625k Contains Ordnance Survey data Crown copyright and database right 2013.

No contemporary metalliferous mining occurs in the UK (EA, 2008) (Bloodworth, Scott & McEvoy 2009) (Natural Environment Research Council 2010). Current threats stem from the legacy of abandoned mines located in catchments draining into the bay (Figure 1.8).

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Figure 1.8 Map showing the location of abandoned mines within the catchment areas of rivers and streams draining into the Ulverston Channel. Created using ESRI ArcMap 10.0. Data sources: (1) EDINA Ordnance Survey Miniscale 1:1 000 000 Contains Ordnance Survey data Crown copyright and database right 2013. (2) European Commission Joint Research Centre Institute for Environment and Sustainability Catchment Characterisation Modeling River and Catchment Database Version 2.1.

Mines in Cumbria have contributed to increased inputs of heavy-metals to lakes via inflow streams (Davison et al. 1985; Haworth 1992). Coniston and Greenburn mines have a long history of mining for copper-containing minerals such as chalcopyrite and malachite (Arnold, Hodson & Langdon 2008). Their tailings pose the greatest risk of contamination to ecosystems in the vicinity and downstream. Chalcopyrite dissolution

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releases aqueous copper which can precipitate into secondary minerals or be transported downstream (Kimball et al. 2009). The general reaction is

Sediment cores of Coniston Water taken by Davison et al. (1985) show a clear record of mining activity, with raised levels of copper and iron found. Tipping et al. (1997) also found highly-enriched levels of copper and zinc in the sediment of Coniston Water compared to Blelham Tarn, which drained areas unaffected by mining activities. Maberly et al. (2011) conducted the first systematic survey of heavy-metals in the water bodies of Cumbria. Elevated copper concentrations were found in Coniston Water suggesting that tailings from Coniston Copper Mine are still discharging metals into the local hydrological cycle. 1.5.3 Background levels of Cu, Zn and Pb Ascertaining background levels of metals can be challenging in areas draining naturallymineralised zones that also have a long history of human development (Franklin & Jones, 1994). Since 1968, the British Geological Survey (BGS) has been undertaking the analysis of soil and stream sediment nationwide as part of their G-Base programme (Johnson et al. 2005). This project intends to provide a national capability in baseline geochemical mapping (NERC, 2013). Looking more closely at data on metal concentrations found in streams and rivers within Cumbria, it is possible to estimate the concentrations that may be found in the saltmarshes within the Ulverston Channel. The use of Geographical Information Systems (GIS) in applying interpolation techniques to raw data can create spatial prediction maps to which results can be compared to (Figures 1.9 - 1.11). 44

Figure 1.9 Cu concentrations (g g-1) at different locations with the catchment areas draining into the Ulverston Channel, Morecambe Bay and the results of a Radial Basis Function interpolation map generated to predict the possible concentrations found at each sampling site. Created using ESRI ArcMap 10.0. Data source: (1) G-BASE stream sediment sampling (Johnson et al. 2005). (2) European Commission Joint Research Centre Institute for Environment and Sustainability Catchment Characterisation Modeling River and Catchment Database Version 2.1. (3) EDINA Imagery Basemap. Contains Ordnance Survey data Crown copyright and database right 2013.

High Cu concentrations can be found around the mineralised zones and associated mines. Downstream of Coniston Water concentrations fall back to the low levels seen in first and second order streams unaffected by mining activities, confirming the findings by (Tipping et al. 1997). Sampling of streams flowing into the mid-estuary show low levels between 10.87-35.81g g-1.

Radial Basis Function interpolation predicts that both sites will have mean concentrations of copper below 20g g-1 (Figure 1.9)

45

Figure 1.10 Zn concentrations (g g-1) at different locations with the catchment areas draining into the Ulverston Channel, Morecambe Bay and the results of a Radial Basis Function interpolation map generated to predict the possible concentrations found at each sampling site. Created using ESRI ArcMap 10.0. Data source: (1) G-BASE stream sediment sampling (Johnson et al. 2005). (2) European Commission Joint Research Centre Institute for Environment and Sustainability Catchment Characterisation Modeling River and Catchment Database Version 2.1. (3) EDINA Imagery Basemap. Contains Ordnance Survey data Crown copyright and database right 2013.

Extremely high zinc concentrations can be found close to Penny Rig Quarry and also near the mouth of the estuary. Again, downstream of Coniston Water concentrations fall back to the lower levels seen in first and second order streams outside the mineralised zone. Coniston Water is effectively acting as a sink for the heavy-metals (Tipping et al. 1997). Streams flowing into the mid-estuary show low levels between 65-1201.71 g g1.

Radial Basis Function interpolation technique predicts that the mean concentration for Plumpton will fall between 300-450g g-1 and between 220-450g g-1 at Plumpton Hall (Figure 1.10) 46

Figure 1.11 Pb concentrations (g g-1) at different locations with the catchment areas draining into the Ulverston Channel, Morecambe Bay and the results of a Radial Basis Function interpolation map generated to predict the possible concentrations found at each sampling site. Created using ESRI ArcMap 10.0. Data source: (1) G-BASE stream sediment sampling (Johnson et al. 2005). (2) European Commission Joint Research Centre Institute for Environment and Sustainability Catchment Characterisation Modeling River and Catchment Database Version 2.1. (3) EDINA Imagery Basemap. Contains Ordnance Survey data Crown copyright and database right 2013.

Lead concentrations are high in the upper catchment area and extremely high near Penny Rig Quarry. Downstream of Coniston Water concentrations fall dramatically. Streams flowing into the mid-estuary show levels between 17.36-257.99 g g-1.

Radial Basis Function interpolation predicts that both sites will have mean concentrations of lead below 45g g-1 (Figure 1.11).

Interestingly, all heavy-metals were found in their lowest concentrations in streams relatively near each marsh. Site 5167 opposite Plumpton Marsh had significantly 47

reduced values compared to most sites within the dataset. Similarly site 4718 down the estuary from Plumpton Hall generally showed a lower concentration of each metal than others in the dataset. These particular sites may provide the closest comparable site to the study area and to Plumpton particularly due to its sheltered location. 1.5.4 Pollution in Morecambe Bay Despite a long history of human habitation around Morecambe Bay it is not highly urbanised at the coastline with fragmented human development centred on Morecambe, Grange-over-Sands, Heysham and Barrow-in-Furness (Centrica, 2012). Active ports exist at the former two locations and a defunct one at previously landlocked Ulverston, which was connected to the sea by the Ulverston Canal in the late 18th century (Priestley, 1831). It thrived until the advent of the railway age when demand for its use waned drastically and it eventually fell in to disrepair. It was recently acquired by Glaxosmithkline who own a factory adjacent to the canal. The factory originally released untreated waste into the Bay (Robinson 1987). Other historic activities in the area with considerable pollution impact include the effluent resulting a wartime munitions factory and the chlor-alkali industry (MAFF 1994). Other contemporary pollution sources include offshore gas fields and Heysham Nuclear Power Station. Until 1997, macerated untreated sewage was released into the Bay (Jones & Obiri-Danso, 1999) but nowadays a 2.5 km outfall pipe from Middleton Sewage Works extends into the bay south of Heysham harbour. Heavy-metals accumulate in water used in power generation.

48

1.5.5 Heavy-metal deposition at Cockley Beck (NY247015) There are two non-automatic metal monitoring networks in the UK. The Urban and Industrial Metals Network (UIMN) and the Rural Heavy Metals Network (RHMN), which are currently managed and operated for Defra and the devolved administrations in the UK by the National Physical Laboratory (NPL9) and Centre for Ecology & Hydrology (CEH10) respectively. Cockley Beck is the station closest to the study area. Graphs of average annual Cu, Zn and Pb deposition are presented below (Figures 1.12 & 1.13).

4.0

Volume weighted rain/cloud concentrations (g l-1)

3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 2004 2005 2006 Year 2007 2008 2009 Pb Zn Cu

Figure 1.12 Line chart showing the mean rain/cloud concentrations of Cu, Zn & Pb measured at Cockley Beck from 2004-2005. 7.000 Air concentrations (ng m3) 6.000 5.000 4.000 3.000 2.000 1.000 0.000 2004 2005 2006 2007 Year Figure 1.13 Line chart showing the mean concentration in air of Cu, Zn & Pb measured at Cockley Beck from 2004-2005. 2008 2009 Cu Zn Pb

10

National Physical Laboratory Centre for Ecology & Hydrology, part of the Natural Environment Research Council.

1.5.6 Saltmarsh in Morecambe Bay Morecambe Bay EMS has over 5% of the UKs total saltmarsh (Gray & Scott 1987) (Tuley, Cranbrook & Yates 1996). Forming a discontinuous fringe around the bay, saltmarshes are particularly well established within the estuaries of the Rivers Wyre, Lune, Kent and Leven (Pringle 1995). The mean spring tidal range of 10.5m and mean neap tidal range of 3.4m influences the distribution of saltmarshes which are generally only found within the upper 2.5m of the intertidal range (Gray & Scott 1987)(French & Livesy 2000). The majority have sandy substrates and are grazed by livestock, giving them a unique character (Gray & Scott 1987). They are classified phytogeographically as typical west-coast (Type B) marshes by Adam (1978), who also highlighted the difficulty of separating the effects of livestock grazing and substrate type in governing the phytosociological relationships in many British saltmarshes. Less than 1% of saltmarsh in Morecambe Bay had been ungrazed up to 1974 and this has been the dominant factor affecting the communities of vegetation found there (Robinson 1987). The saltmarshes of the Bay are renowned for their golf course look, typified by low swards of persistent grasses (Gray & Scott 1987). Morecambe Bay is a sink for sediment and saltmarsh development is currently accretional (French & Livesey 2000)(Joint Nature Conservation Committee (JNCC) 2004). Approximately 400ha of marsh developed between 1845-1967 but heavy losses have also occurred in other areas such as documented in the Kent Estuary by Pringle (1995). Fluctuating patterns of erosion and accretion have been attributed to the shifting low-water river channels (Gray 1972) (Gray & Scott 1987) (Pringle 1995).

Figure 1.14 The development of estuarine saltmarsh in the Ulverston Channel (Leven Estuary) and Kent Estuary (Gray & Scott 1987).

MATERIALS AND METHODS

The concentrations of Cu, Zn and Pb and physicochemical parameters such as pH(water), Electrical Conductivity (EC1:5), moisture content (%) and organic matter (LOI%) were measured and comparisons made between marshes. Statistical differences in variables and any relationships or trends relating to them were explored and discussed. Interpolation prediction maps were constructed for metals close to or exceeding any SQG levels.

2.1

Description of the Study Area

Plumpton (SD324801) and Plumpton Hall (SD314786) saltmarshes are located in the Ulverston Channel draining into the north of Morecambe Bay (Figure 2.1).

Figure 2.1 Map detailing the catchment areas of the main rivers and streams flowing into the Ulverston Channel which drains into the north of Morecambe Bay, UK. Created using ESRI ArcMap 10.0.

Each saltmarsh represents a sampling site chosen for their specific characteristics. Both are estuarine marshes located in the Ulverston Channel. They differ in size, hey are separated by a railway viaduct Plumpton Hall is a rare example of an ungrazed saltmarsh in Morecambe Bay. Plumpton saltmarsh is intensively grazed by sheep. 2.2 Sampling procedure

Sampling proceeded at dawn on 3rd February 2013 after a high-tide at Ulverston of 8.20m at 03:58. 2.2.1 Sampling point generation The coordinates for the centre of each saltmarsh were determined using the Latitude and Longitude of a Point online tool (iTouchMap.com, 2012)(Figure 2.2).

Figure 2.2 Map showing the coordinates for the centre of Plumpton Marsh (iTouchMap.com, 2012)

Inputting the coordinates into the Random Point Generator online tool (GeoMidpoint.com, 2013) and setting the parameters No. of points to 1000 and Max distance to 1km generated 1000 random sampling points (Figure 2.3).

53

Figure 2.3 Map showing the 1000 randomly generated sampling points for Plumpton Marsh

Coordinates were input into ESRI ArcMap 10.0 and clipped to a polygon shapefile relating to the surface area of each saltmarsh. This restricted the potential sampling sites to those found on the saltmarsh surface. Sampling proceeded at the first 30 accessible points, located by inputting coordinates into a Garmin GPSmap 62. 2.2.2 Sampling procedure at each sampling point An averaged GPS waypoint and any relevant observations were recorded before sample extraction began (Figure 2.4)

Figure 2.4 Map showing the location of Plumpton and Plumpton Hall saltmarshes and the 30 randomly generated points per site where sampling took place. Created using ESRI ArcMap 10.0 with Bing basemap.

150 300 Metres 600

75 150 Metres

300

54

At each point a composite sample consisting of five increments was taken (Figure 2.5).

Figure 2.5 Photograph showing the pattern of increments that were taken in a 10cm by 10cm plot at each sampling point.

An increment consisted of one load from a 22.86cm (=1.748cm) JMC wet sampling tube attached to a JMC Handle (Appendix 2). Increments were immediately deposited in pre-labelled polythene bags, sealed and stored in a cool bag < 4C for transport to the laboratory. 2.3 Laboratory procedure Brackenhurst Campus laboratory (The Bramley Building) Each composite sample was mixed thoroughly for homogeneity and split into two. One sub-sample was used to determine pH, electrical conductivity (EC), moisture content (%) and organic matter (%) by Loss On Ignition. pH and EC of all 30 sampling points per marsh were determined concurrently by mixing 10g of sub-sample with 50ml distilled water (16M-cm) (ratio 1:5) and recording the measurement provided by a Hanna Combo HI98129 meter at the beginning, middle and end of a 30 minute period. For 15 sampling points moisture content(%) was determined by reweighing 10g of sub-sample after oven-drying for 24h at 105C. Organic matter(%) was calculated by reweighing the dry sample after LOI for 24h at 600C. All analyses were triplicated to provide a mean value for each sampling point (Appendix 3: Raw Primary Data).

55

15 sampling points per marsh from the second sub-sample was prepared for acid digestion by air-drying for seven days followed by 24h oven-drying at 105C. The dessicated sample was then ground using a pestle and mortar, passed through a 63m sieve and stored in fresh, pre-labelled polythene bags ready for transport to Clifton campus. Clifton Campus laboratory (Rosalind Franklin Building) Duplicates of homogenized sub-sample of the <63m fraction were acid-digested for each sampling point. Various studies have found heavy-metals to have an affinity for fine particulates and this fraction represents the best reflection of anthropogenic pollution (Mukherjee & Kumar 2012). 500mg was weighed and placed in an acidwashed PTFE conical flask. 10ml of aqua regia (1:3 HNO3:HCl) was added slowly and the flask placed on a hot plate at 180 C for 24h. The reduced supernatant was mixed with ultrapure water (18M-cm) and filtered through Whatman No.1 (=125mm) filter paper into a 100ml volumetric flask. Filling to volume gave a dilution factor of 200. The sample was decanted into 15ml and 50ml Autosampler cartridges for analysis and storage respectively. 2.4 Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) Heavy-metal analysis was conducted using a PerkinElmer Optima 2100 DV ICP-OES machine (Shelton, CT, USA) with WinLab32 for ICP software, enabling synchronized measurement of the analyte wavelengths of interest. Quality control measures included analysis of prepared blanks and standards with matrices matching the unknown samples. All calibrations had an R2 value higher than the desired 0.995 (Table 16).

56

Table 16 Statistics and results for each element analysed using ICP-OES

Element Cu Zn Pb

Wavelength (nm) 327.393 206.2 220.353

Standards (ppm) 0.2; 0.5; 1; 5; 10; 20 0.2; 0.5; 1; 5; 10; 20 0.2; 0.5; 1; 5; 10; 20

R2 0.99971 0.99995 0.99990

RSD% 0.8589428 1.890046977 1.188729783

Detection Limit (g ml-1) 0.001 0.002 0.003

RSD% was < 2 for all calibrations. Sample analysis precision was much more varied with RSD% values of 2.48(Cu), 0.90(Zn) and 114.32(Pb). Duplicate analysis provided measurements in mg l-1 which were averaged and converted to mg kg-1 using the following formula.
[ [ ] [ ] [ ] ]

2.5 Statistical techniques Statistical analysis was conducted using Microsoft Excel and Minitab 16.2.2 programs. Descriptive statistics and graphical representation helped summarise and visualise the data. Normality of datasets was determined by Kolmogorov-Smirnov tests. Non-parametric data was converted to a normal distribution by square-rooting the values. Some datasets were not convertible and thus non-parametric statistical techniques were applied to these. Two-sample t-tests and Mann-Whitney U-tests were conducted to ascertain whether significant differences exist between all variables at each site. For correlations and relationships between heavy-metals and soil parameters the data from both saltmarshes was pooled to enable more conclusive findings. Pearsons Product Moment and Spearmans Rank tests were then conducted to establish whether significant correlations existed between any variables. Regression and bivariate regression analyses were conducted on parametric variables displaying significant correlations to determine whether significant relationships existed between them. Nonparametric variables were converted using the x transformation and are 57

denoted by a ^ next to the variable symbol (e.g. Pb^). Regression analysis was not possible with Cu as a variable as the dataset could not be converted to a Gaussian distribution by either or log10 transformations and was therefore unsuitable for parametric tests. 2.6 Geographical Information Systems (GIS) Geographical Information Systems (GIS) are increasingly used in a variety of disciplines. GIS can visualize and represent data in different forms and the ability to input, manipulate and spatially analyse primary data is valuable in environmental science, particularly with respect to research into the spatial distribution of pollutants. GIS thus provide a useful tool to assist management and remediation plans by providing information on sources, depositional trends and mobilisation of pollutants. Interpolation techniques and maps were used to predict and visualise the distribution of different variables at each site.

58

RESULTS

Mean values of soil parameters and heavy-metal concentrations in both marshes are summarised in Table 17.
Table 17 Results for each site. Mean standard deviation. Variable (units) n pH(water) EC (S cm-1) Moisture Content (%) LOI (%) Cu (mg kg-1) Zn (mg kg-1) Pb (mg kg-1) 30 30 15 15 15 15 15 Plumpton Marsh (P) Mean Std Dev 8.60 0.41 613 204 27.56 3.90 4.90 1.22 17.47 3.06 38.39 19.76 5.64 1.63 Min 7.46 285 22.43 2.74 14.33 12.06 4.24 Max 9.28 919 35.05 6.93 25.90 82.87 10.44 Plumpton Hall Marsh (S) Mean Std Dev 8.42 0.38 958 327 35.20 9.58 6.50 + 2.41 17.55 2.34 37.69 11.36 6.70 2.22 Min 7.77 127 21.73 3.99 14.43 17.50 3.75 Max 9.07 1367 59.80 12.74 23.08 58.30 10.52

3.1 Heavy-metals Magnitudes of heavy-metals in both marshes followed the order Zn>Cu>Pb with mean concentrations of 38.39 mg kg-1 (Zn), 17.47 mg kg-1 (Cu) and 5.64 mg kg-1 (Pb) for Plumpton, and 37.69 mg kg-1 (Zn), 17.55 mg kg-1 (Cu) and 6.70 mg kg-1 (Pb) for Plumpton Hall (Figures 3.13.3).
90 80 70 60 50 40 30 20 10
5.64 17.47 17.55 38.39 37.69

Concentration (mg kg-1)

6.70

P_Cu

S_Cu

P_Zn

S_Zn

P_Pb

S_Pb

Figure 3.1 Bar chart with error bars (95% Confidence Interval for the mean) and individual data plots showing the mean concentrations of each heavy-metal at each sampling site, where P_ = Plumpton Marsh and S_ = Plumpton Hall Marsh.

59

3.1.1 Plumpton saltmarsh (SD324801)

13

11

10 14

9 8

15 16

6 5 17 18

20 19 21 4 22

3 25 26 27 28 30 2 29 1 24

23

90 80

Concentration (mg kg-1)

70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Sampling Point Cu Zn Pb

Figure 3.2 Map and column chart with standard error bars showing the location and mean concentration of Cu, Zn and Pb at each sampling point at Plumpton marsh.

60

3.1.2 Plumpton Hall saltmarsh (SD314786)

19 12 13 14

16 15

18

17

11

20 10 21

9 29 23 1 28 30 2 24 27 25 26 4 5 6 7 3

22

90 80

Conentration (mg kg-1)

70 60 50 Cu 40 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Sampling Point Zn Pb

Figure 3.3 Map and column chart with standard error bars showing the location and mean concentration of Cu, Zn and Pb at each sampling point at Plumpton Hall marsh.

61

3.2 Soil parameters pH(water) of both saltmarshes was alkaline with mean values of 8.60 and 8.42 for Plumpton and Plumpton Hall respectively. The EC(1:5) was low at both marshes with mean values of 613204 Siemens cm-1 for Plumpton and 958327 Siemens cm-1 for Plumpton Hall. The moisture content at both marshes was over 20% and reached over 40% in places at Plumpton Hall. 3.2.1 Plumpton saltmarsh (SD324801) pH
10 8 8.93 8.30 8.30 9.03 8.82 8.85 8.65 8.75 9.05 8.80 8.54 8.19 8.20 8.72 8.70

pH

6 4 2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Sampling Point

Figure 3.4 Column chart with standard error bars showing the mean pH for each sampling point at Plumpton saltmarsh.

Electrical Conductivity
1400 1204

EC (Siemens cm-1)

1200 1000 800 600 400 200 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Sampling Point 762 686 611 410 647 536 530 427 471 438 659 701 683 667

Figure 3.5 Column chart with standard error bars showing the mean EC for each sampling point at Plumpton saltmarsh.

62

60

Moisture Content (%)

50 40 30 20 10 0 1 2 31.01 26.12

35.05 31.81 23.09 24.27 24.46 31.07

28.17 29.06 26.41 31.53 22.43 26.33 22.66

10

11

12

13

14

15

Sampling Point
Figure 3.6 Column chart with standard error bars showing the mean moisture content (%) for each sampling point at Plumpton saltmarsh.

14 12 10 LOI(%) 8 6 4 2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Sampling Point

Figure 3.7 Column chart with standard error bars showing the mean organic matter (%) deduced by LOI for each sampling point at Plumpton saltmarsh.

6.93 6.82 4.61 5.18 3.86 5.44 4.67 5.61

6.52

4.80 4.34

3.39

4.80

3.83

2.74

3.2.2 Plumpton Hall saltmarsh (SD314786)

10 8 8.32 8.79 8.33 8.60 8.49 7.90 8.39 8.80 9.00 8.31 8.44 8.55 8.68 8.22 8.19

pH

6 4 2 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Sampling Point

Figure 3.8 Column chart with standard error bars showing the mean pH for each sampling point at Plumpton Hall saltmarsh.

63

Electrical Conductivity
1600 1400 1456 1184 975 922 490 625 451 1120 1060 864 1306 1141 1000 786 943

EC (Siemens cm-1)

1200 1000 800 600 400 200 0 1

10

11

12

13

14

15

Sampling Point
Figure 3.9 Column chart with standard error bars showing the mean EC for each sampling point at Plumpton Hall saltmarsh.

59.80 60 45.77 38.96 26.57 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Sampling Point

Figure 3.10 Column chart with standard error bars showing the mean moisture content (%) for each sampling point at Plumpton Hall saltmarsh.

Moisture Content (%)

50 40

40.45 34.46 29.59 36.32 33.15 28.16 21.73 33.78 31.77 24.65

42.90

14 12 10 LOI(%) 8 6 4 2 0 1 2

12.74 9.87 8.00 6.80 4.39 6.43 5.01 5.54 5.50 4.62 3.98 6.35 5.14 4.52 8.62

10

11

12

13

14

15

Sampling Point
Figure 3.11 Column chart with standard error bars showing the mean organic matter(%) deduced by LOI for each sampling point at Plumpton Hall saltmarsh.

64

3.3 Differences 3.3.1 Heavy-metals There was no significant difference between copper concentrations at each marsh (Mann-Whitney test, W=218.0, n=15, p=0.5614)(Figure 3.12).
18.5 17.47 17.55

Cu conc. (mg kg-1)

18.0 17.5 17.0 16.5 16.0 Plumpton Plumpton Hall

Figure 3.12 Bar chart with standard error bars showing the mean concentration of Cu at each sampling site (n=15).

No significant difference in zinc concentrations was found between sites (two-sample t(22)=0.12, n=15, p=0.908)(Figure 3.13).
46 44 42 40 38 36 34 32 30 38.39 37.69

Zn conc. (mg kg-1)

Plumpton

Plumpton Hall

Figure 3.13 Bar chart with standard error bars showing the mean concentration of Zn at each sampling site (n=15).

There was no significant difference between lead concentrations at each marsh (MannWhitney test, W=199.0, n=15, p=0.1711)(Figure 3.14).

65

7.5

6.70

Pb conc. (mg kg-1)

7.0 6.5 6.0 5.5 5.0 4.5 4.0 Plumpton Plumpton Hall 5.64

Figure 3.14 Bar chart with standard error bars showing the mean concentration of Pb at each sampling site (n=15).

3.3.2 Soil parameters No significant difference in pH was found between sites (two-sample t(57)=1.75, p=0.086, n=30 (Figure 3.15).
8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 Plumpton Plumpton Hall 8.60 8.42

Figure 3.15 Bar chart with standard error bars of the mean pH at each sampling site (n=30).

A significant difference was found between the EC at each site, Plumpton Hall having a significantly higher mean value (twosample t(48)= -4.90, p<0.001, n= 30)(Figure 3.16).
1200 958

EC (Siemens cm-1)

pH

1000 800 600 400 200 0 Plumpton Plumpton Hall 613

Figure 3.16 Bar chart with standard error bars of the mean Electrical Conductivity at each sampling site (n=30).

66

Plumpton Hall moisture content was also significantly higher than that of Plumpton (two-sample t(18)= -2.86, p=0.010, n=15)(Figure 3.17).
40 30 27.56 35.20

MC (%)

20 10 0 Plumpton Plumpton Hall

Figure 3.17 Bar chart with standard error bars of the mean Moisture Content(%) at each sampling site (n=15).

A significant difference was found between the organic matter at each site, Plumpton Hall again having statistically higher levels (twosample t(20)= -2.29, p=0.033, n= 15)(Figure 3.18).

8 6 4.90

6.50

LOI(%)

4 2 0 Plumpton Plumpton Hall

Figure Figure 3.18 Bar chart with standard error bars of the mean Loss On Ignition(%) at each sampling site (n=15).

3.4 Correlation analyses 3.4.1 Pooled data Correlation analyses conducted between all variables of the pooled data can be found in Table 18. 67

Table 18 Correlations between all measured variables (pooled data).

pH EC MC% LOI% Cu Zn Pb

pH 1

EC -0.096 1

MC -0.650*** 0.102 1

LOI% -0.468** 0.250 0.894** 1

Cu -0.403* 0.128 0.657** 0.660** 1

Zn -0.551** 0.037 0.496** 0.710** 0.785** 1

Pb -0.364* 0.116 0.554** 0.558** 0.797** 0.776** 1

* Indicates significant correlation at the 0.05 level (2-tailed). ** Indicates significant correlation at the 0.01 level (2-tailed). *** Indicates significant correlation at the 0.001 level (2-tailed).

Soil parameters All heavy-metals had significant or very significant negative correlations with pH (Figure 3.19).
90 80 70 Concentration (mg kg-1) 60 50 Cu 40 30 20 10 0 7.00 7.50 8.00 pH
Figure 3.19 Scatterplot with regression trendlines showing the correlation of Cu, Zn and Pb with pH.

y = -29.513x + 290.69 R = 0.304

Zn y = -2.0465x + 35.029 R = 0.0513 y = -2.2111x + 25.097 R = 0.1088 Pb

8.50

9.00

9.50

No significant correlation was observed between EC and any heavy-metal. All heavymetals had very significant positive correlations with moisture content (Figure 3.20).

68

100 90 80

Concentration (mg kg-1)

70 60 50 40 30 20 10 0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0

y = 0.9613x + 7.869 R = 0.246

Cu Zn Pb y = 0.1368x + 13.216 R = 0.1749 y = 0.1272x + 2.1755 R = 0.2747

60.0

65.0

Moisture Content (%)

Figure 3.20 Scatterplot with regression trendlines showing the correlation of Cu, Zn and Pb with moisture content (%).

All heavy-metals had very significant positive correlations with organic matter (Figure 3.21).
70 60 Concentration (mg kg-1) 50 40 Cu 30 20 10 0 0.0 2.0 4.0 6.0 8.0 LOI(%)
Figure 3.21 Scatterplot with regression trendline showing the correlation of Cu, Zn and Pb with LOI(%).

y = 3.5352x + 7.9317 R = 0.3133

y = 0.5217x + 14.535 R = 0.1595 y = 0.4782x + 3.4422 R = 0.2434

Zn Pb

10.0

12.0

14.0

16.0

69

Heavy-metals All individual heavy-metals had very significant positive correlations with each other (Figures 3.22 - 3.24).
100 90 80 70 y = 3.4282x - 21.987 R = 0.3348

Zn/Pb (mg kg-1)

60 50 40 30 20 10 0 10 15 20 Cu (mg kg-1) 25 30 35 y = 0.4651x - 1.9745 R = 0.3927 Cu/Zn Cu/Pb

Figure 3.22 Scatterplot with regression trendlines showing the correlation of Cu with Zn and Pb.

30

25 y = 0.0977x + 13.795 R = 0.3348

Cu/Pb(mg kg-1)

20

15

Zn/Cu Zn/Pb

10 y = 0.0837x + 2.9836 R = 0.4468 5

0 0 20 40 Zn (mg kg-1)
Figure Figure 3.23 Scatterplot with regression trendlines showing the correlation of Zn with Cu and Pb.

60

80

100

70

30

25

y = 0.0977x + 13.795 R = 0.3348

20

Cu/Pb(mg kg-1)

15

Zn/Cu Zn/Pb

10 y = 0.0837x + 2.9836 R = 0.4468 5

0 0 10 20 30 40 50 Zn (mg kg-1) 60 70 80 90 100

Figure 3.24 Scatterplot with regression trendlines showing the correlation of Pb with Cu and Zn.

3.4.2 Plumpton Marsh (SD324801)

Table 19 Correlations between all measured variables and their coefficients at Plumpton Marsh.

pH EC MC% LOI% Cu Zn Pb

pH 1

EC -0.051 1

MC% -0.674** 0.075 1

LOI% -0.438 0.078 0.772** 1

Cu -0.240 -0.036 0.664** 0.606* 1

Zn -0.630* -0.004 0.883*** 0.699** 0.779** 1

Pb -0.028 -0.114 0.354 0.376 0.764** 0.6535* 1

* Indicates significant correlation at the 0.05 level (2-tailed). ** Indicates significant correlation at the 0.01 level (2-tailed). *** Indicates significant correlation at the 0.01 level (2-tailed).

A very significant negative correlation was found between pH and moisture content (Spearmans rs(13)=-0.674, p<0.01). A very significant positive correlation was found between moisture content and organic matter (Pearsons r=0.772, n=15, p=0.001). A very significant positive correlation was found between moisture content and Cu (Spearmans rs(13)=0.664, p<0.01). An extremely significant positive correlation was found between moisture content and Zn (Pearsons r=0.883, n=15, p=0.000). A significant 71

positive correlation was found between organic matter and Cu (Spearmans rs(13)=0.606, p<0.05). A very significant positive correlation was found between organic matter and Zn (Pearsons r=0.699, n=15, p=0.004). 3.4.3 Plumpton Hall Marsh (SD314786)
Table 20 Correlations between all measured variables and their coefficients at Plumpton Hall Marsh.

pH EC MC% LOI% Cu Zn Pb

pH 1

EC 0.270 1

MC -0.615* -0.299 1

LOI% -0.486 -0.235 0.963*** 1

Cu -0.312 0.325 0.671** 0.646* 1

Zn -0.572* 0.149 0.623* 0.551* 0.796** 1

Pb -0.310 -0.037 0.462 0.426 0.768** 0.788** 1

* Indicates significant correlation at the 0.05 level (2-tailed). ** Indicates significant correlation at the 0.01 level (2-tailed).

*** Indicates significant correlation at the 0.001 level (2-tailed).

A very significant negative correlation was found between pH and moisture content Pearsons r=-0.615, n=15, p=0.015). No significant correlation was found between organic matter and Pb (Pearsons r=0.426, n=15, p=0.113). A significant positive correlation was found between organic matter and Cu (Spearmans rs(13)=0.6464, p<0.02). For Zn, a significant positive correlation with organic matter was observed (Pearsons r=0.551, n=15, p=0.033). 3.5 Regression Analysis 3.5.1 Pooled data pH Regression analysis showed a very significant negative relationship between pH and Zn (Zn = 291 29.5 pH, F1,28=12.23, p=0.002, r2=0.304)(Figure 3.25) but no significant relationship between pH and Pb^ (Pb^ = 6.17 - 0.434 pH, F1,28=3.54, p=0.070, r2=0.112).

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90 80 70 60 Zn (mg kg-1) 50 40 30 20 10 0 7.6 7.8 8 8.2 8.4 pH 8.6 8.8 9 9.2 9.4
Figure 3.25 Scatterplot with regression trendlines showing the significant negative relationship between pH and Zn.

y = -29.513x + 290.69 R = 0.304

A very significant positive relationship was found between pH and organic matter^ (pH = 9.47 - 0.388 LOI^, F1,28=10.34, p=0.003, r2=0.270). Moisture Content An extremely positive significant relationship was found between moisture content and pH (pH = 9.30 - 0.0235 MC, F1,28=20.43, p<0.001, r2=0.422) and also between moisture content and organic matter^ (LOI^ = 0.947 + 0.0449 MC, F1,28=168.02, p<0.001, r2=0.857).

Regression analysis showed a very significant positive relationship between moisture content and Zn (Zn = 7.9 + 0.961 MC, F1,28=9.14, p=0.005, r2=0.246) and also between moisture content and Pb^ (Pb^ = 1.67 + 0.0249 MC, F1,28=10.91, p=0.003, r2=0.280).

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100 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 Moisture Content (%) 50 60 70 y = 0.9613x + 7.869 R = 0.246

Zn (mg kg-1)

Figure 3.26 Scatterplot with regression trendlines showing the significant positive relationship between Moisture Content (%) and Zn.

Organic matter There was a significant positive relationship between organic matter and pH (pH = 9.47 - 0.388 LOI^, F1,28=10.34, p=0.003, r2=27.0) and also between organic matter and moisture content (MC = - 13.6 + 19.1 LOI^, F1,28=168.02, p<0.001, r2=0.857). 3.5.2 Individual Organic Matter Regression analysis showed a significant positive relationship between organic matter and Zn concentrations at Plumpton (P_Zn = - 17.0 + 11.3 P_LOI, F1,13=12.42, p=0.004, r2=0.4885) and at Plumpton Hall (S_Zn = 20.8 + 2.60 S_LOI, F1,13=5.68, p=0.033, r2=0.3041 )(Figure 3.27).

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90 80 70 Zn concentration (mg kg-1) 60 50 40 30 20 10 0 0.00 2.00 4.00 6.00 LOI(%) Plumpton Plumpton Hall 8.00 10.00 12.00 14.00 y = 2.5978x + 20.806 R = 0.3041 y = 11.29x - 16.965 R = 0.4885

Figure 3.27 Scatterplots with regression trendline showing the correlation between LOI(%) and Zn for both sites.

3.6 Multiple regression A bivariate regression with zinc as dependent variable to pH and organic matter^ showed a significant relationship (Zn = 189 - 21.0 pH + 12.2 LOI^, F1,28=8.00, p=0.002).

A significant positive relationship was found between zinc and the two independent variables of moisture content and organic matter (Zn = - 5.5 + 0.329 MC + 14.1 LOI^, F1,13=4.8 , p=0.016). 3.7 GIS Interpolation Cooper is the only metal displaying concentrations within the vicinity of SQGs. Interpolation maps have been constructed to predict its distribution across Plumpton Marsh which is actively grazed by sheep.

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Inverse Distance Weighting

Figure 3.28 Map displaying the histogram and predicted value contours for Cu using the Inverse Distance Weighting interpolation technique.

76

Global Polynomial Interpolation

Figure 3.29 Map displaying the histogram and predicted value contours for Cu using the Inverse Distance Weighting interpolation technique.

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Kriging/CoKriging

Figure 3.30 Map displaying the histogram and predicted value contours for Cu using the Kriging/CoKriging interpolation technique.

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DISCUSSION

The results suggest that concentrations of copper, zinc and lead in the sediment of Plumpton and Plumpton Hall saltmarshes is minimal. All mean heavy-metal concentrations were below various SGQs (Tables 7 & 8) and low when compared to studies of other anthropogenically impacted estuaries (Tables 12 & 13). The concentrations found for Zn and Pb were much lower than levels predicted utilising stream sediment data in the local area (Johnson et al. 2005)(Figures 1.10 1.11) and comfortably below the bottom end of numerous sediment quality guidelines (Tables 7 & 8). No sampling points on either site had Zn or Pb concentration above their respective
SQUIRT TEL

(Figures 4.1 & 4.2).

TEL 124

120

Conentration (mg kg-1)

100 80 60 40 20 0
TEL 30.2 TEL 18.7

Cu Zn Pb

7 8 9 10 11 12 13 14 15 Sampling Point Figure 4.1 Column chart with standard error bars showing the mean concentrations of Cu, Zn and Pb at Plumpton and corresponding SQUIRT TEL concentrations.

120

TEL 124

Conentration (mg kg-1)

100 80 60 40 20 0
TEL 30.2 TEL 18.7

7 8 9 10 11 12 13 14 15 Sampling Point Figure 4.2 Column chart with standard error bars showing the mean concentrations of Cu, Zn and Pb at Plumpton Hall sampling points and corresponding SQUIRT TEL concentrations.

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In contrast, four sampling points at Plumpton and five at Plumpton Hall had copper concentrations above the SQuiRT TEL of 18.7 mg kg-1 (Buchman 2008) but the figure rises to nine sampling points for Plumpton and 12 for Plumpton Hall when using the ONTARIO LEL of 16 mg kg-1 (Figure 4.3 & 4.4).
35 ERL 34.0

Concentration (mg kg-1)

30 25 20 15 10 5 0 TEL 18.7 LEL 16

7 8 9 10 11 12 13 14 15 Sampling Point Figure 4.3 Column chart with standard error bars showing the mean concentrations of Cu at Plumpton sampling points and corresponding SQUIRT TEL concentrations. 35 ERL 34.0

Conentration (mg kg-1)

30 25 20 15 10 5 0 TEL 18.7 LEL 16

7 8 9 10 11 12 13 14 15 Sampling Point Figure 4.4 Column chart with standard error bars showing the mean concentrations of Cu at Plumpton Hall sampling points and corresponding SQUIRT TEL concentrations.

Zinc concentrations ranged between below the 10th percentile (38 mg kg-1) and just over the median (82 mg kg-1) value of typical concentrations found in the soils of England and Wales (Table 6). At both marshes lead concentrations at all sampling 80

points were below the 10th percentile (20 mg kg-1). The highest zinc concentration, 82.87 mg kg-1 at Plumpton Marsh (sampling point #3), was comfortably below the SQuiRT TEL of 124 mg kg-1. Similarly for lead, the highest concentration, 10.52 mg kg-1 at Plumpton Hall Marsh (sampling point #15), was well below the SQuiRT TEL of 30.2 mg kg1.

Copper concentrations in both marshes were low and ranged between just under the

median (18 mg kg-1) and just above the arithmetic mean (23 mg kg-1) values of typical concentrations found in the soils of England and Wales (Table 6) (Buchman, 2008). However, despite a relatively low mean copper concentration,

The results bear similarities with the low concentrations of heavy-metals in lowerestuarine marshes of the Blackwater estuary, UK reported by Emmerson et al. (1997). The marshes do not appear to be susceptible to high loads of Cu from abandoned mines in the catchment areas draining into the Ulverston Channel. Despite an increased input of heavy-metals to lakes in Cumbria via inflow streams (Davison et al. 1985) fluvial transportation of high amounts of Cu, Zn and Pb does not extend to the lower estuary, much of the load instead being deposited in the sediments of Coniston Water and Windermere (Haworth 1992; Tipping et al. 1997). Another possible explanation for the low levels is the dilution of heavy-metal concentrations by sediments deriving from less-polluted external sources. The principal sediment types of the major channels of Morecambe Bay are fine and very fine sand (60-200m) with finer silt and clay evident in sheltered, low-energy environments (Anderson 1972). Sediment transportation in the Bay is dominated by tidal currents with net direction dictated by flood and ebb tide asymmetry (Centrica, 2012). Sediment is transported into the Bay along the coastline and then outwards in the centre of the Bay (Pringle 1987). Any metal pollution reaching the low estuary could therefore be attenuated by incoming external particulates.

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Investigations into sediment provenance using fingerprinting techniques could elucidate this theory (Rotman et al. 2008). 4.1.1 Organic matter In both saltmarshes organic matter was relatively low with mean values of 4.9% and 6.5% for Plumpton and Plumpton Hall respectively. This is higher than the mean value of 3.2% for saltmarsh sediments of the Karnafully River coast, India (Siddique & Aktar, 2012) but lower than values reported by other studies. Organic matter in sediments of the Tijuana Estuary, California ranged between 8.7% and 13.8% (Weis, Callaway & Gersberg 2001) and (Leendertse, Scholten & van der Wal 1996) found levels of 9.614.8% in Delfzijl and 14.3-16.2% in Marsdiep saltmarsh sediments. The organic matter levels may contribute to the higher EC at Plumpton Hall due to the high CEC of organic matter (Fest et al. 1994). The significant positive relationships between all heavymetals and moisture content could relate to dissolved organic matter within the water (Fest et al. 2008). 4.1.2 Hypotheses Hypothesis #1
H0 The average concentrations of all heavy-metals at Plumpton Hall will not be significantly higher than at Plumpton.

No heavy-metal showed a significantly higher concentration at any site and there is therefore insufficient evidence to reject the null hypothesis. Magnitudes followed the order Zn>Cu>Pb in both marshes and mean concentrations were remarkably similar. The highest copper and zinc concentrations were both found at Plumpton Marsh although zinc perhaps showed a more consistent higher signature across Plumpton Hall saltmarsh (Figures 3.2 & 3.3). 82

Hypothesis #2
H0 Organic matter levels at Plumpton Hall will not be significantly higher than at Plumpton.

Statistical analysis provided evidence to reject the null hypothesis. As expected, organic matter at Plumpton Hall was significantly higher than at Plumpton. It is likely that sheep grazing over many years at Plumpton has affected species composition and resulted in an abundance of low-lying swards of grasses with corresponding reduction in NPP detritus production (Jensen et al., 1985) (Robinson 1987)(Bos et al., 2005). This leads to a reduced incorporation of decaying biomass into the saltmarsh sediment (Silliman, Grosholz & Bertness (eds.) 2009). The higher levels of organic matter did not correspond to an increased loading of any heavy-metal at Plumpton Hall marsh despite the apparently favourable conditions for their retention. Hypothesis #3
H0 There will not be a significant positive relationship between organic matter and all heavy-metals.

Pooled data showed significant positive correlations between organic matter and all heavy-metal but at each saltmarsh the results were more varied. Pb did not correlate significantly with organic matter at Plumpton or Plumpton Hall and Cu did not correlate with organic matter at. Significant positive relationships were observed between organic matter and both Zn and Pb. Organic matter is an important parameter influencing soil buffering capacity for zinc (Dvorak et al., 2003)(Chirwa & Yerokun, 2012). Despite studies highlighting the link between organic matter and increased retention of heavy-metals, Bai et al. (2012) found a significant correlation between organic matter and Cu, Zn and Pb in tidal freshwater marshes but no significant correlation between organic matter and any heavy-metals in tidal saltmarshes. It is possible that at elevated salinities the brackish waters found in estuaries occupy sorption sites on organic substances and they are less available to metals. 83

Hypothesis #4
H0 There will not be a significant negative correlation between pH and all heavy-metals.

Statistical analysis showed pH to have a significant relationship with all heavy-metal concentrations and there is therefore sufficient evidence to reject the null hypothesis. pH is the factor that mostly strongly influences the adsorption, retention and mobility of heavy-metals in various compartments (Calmano, Hong & Frstner 1993; Pierzynski, Sims & Vance 2000; de Matos et al. 2001; Bhargava et al. 2012). The mobility of copper , zinc and lead all increase with decreasing pH (Kumpiene, Lagerkvist & Maurice 2008) The alkalinity of both marshes is likely to restrict the mobility of heavy-metals within the saltmarsh sediment and soil. 4.2 Assumptions The theoretical foundation dictated that elevated levels of heavy-metals can be found in the sediment of saltmarsh communities close to or connected to pollution sources. It assumes that intensive grazing by livestock profoundly influences the vegetation within a saltmarsh and that these factors would influence other areas. Every piece of instrumentation used in the analysis was calibrated by a trained person prior to use and was capable of detecting each analyte within the limit of detection (LOD) expected. The effect of spectral interference on the ICP-OES was reduced by choosing non-interfering wavelengths to measure the analytes. The use of open digestion is suitable in this study as volatile substances such as mercury are not being analysed. Assumptions are made that no contamination of samples has occurred, whether via the analyst, reagent or apparatus.

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4.3 Limitations Despite the measures taken to homogenise each sample the imperfections in each technique and the inherent heterogeneity of the sediment leads to fundamental error (FE) which cannot be controlled. Assumptions are made that digestion of each sample is complete and comparable. Samples were not collected or digested in an oxygen-free environment and metal sulphides may have been oxidised during storage.

The unique conditions of the study area mean that the generalisability of the study is low. The results would be difficult to extrapolate in situations anywhere outside or even within Morecambe Bay. 4.4 Improvements to the study Increasing the sample size to minimum of 30 for each site would increase the accuracy of findings and reduce grouping and segregation errors associated with random sampling. A lower dilution factor would reduce the chance of error margins associated with ICP-OES analysis.

CONCLUSION

No significant difference in metal loading could be distinguished between grazed and ungrazed estuarine saltmarsh communities despite significant differences in soil parameters. The findings indicate that copper, zinc and lead pollution in the lowestuarine saltmarshes of the Ulverston Channel is minimal. Heavy-metal pollution may be diluted by incoming sediment from less polluted external sources. The alkalinity of the soils and sediment suggest that any hotspots of metal concentrations within the estuary are likely to be relatively stable with low bioavailability.

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1.1

Recommendations for further research

There are numerous options for future research. This study looked at homogenized surface samples down to 22.86 cm. Depending on the accretion rate at each site this can represent anything in the order of tens to hundreds of years of particulate deposition. Looking at changes in concentrations with incremental depth would enable chronological depositional trends to be investigated and may reveal horizons related to periods when deposition was elevated. Including marshes higher up the estuary would provide further data to help explain the low concentrations of all metals found at both sites.

The pseudototal provided by aqua regia digestion is less useful in assessing risk to biota (Spencer & MacLeod 2002). Undertaking a sequential extraction to analyse the labile fraction can aid research into the uptake of heavy-metals by plants and potential introduction to grazing herbivores (Tessier, Campbell & Bisson 1979).

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7 APPENDIX 1: MINES IN CUMBRIA

# 1 2 3 4 5 6 Name Goldscope Copper Mine Coniston Copper Mine Greenside Lead Mine Carrock Mine Force Crag Mine Roughton Gill Mine Driggeth Mine Florence Mine OS Grid Ref NY228185 SD285987 NY364171 NY323330 NY200216 NY305375 Minerals Chalcopyrite (CuFeS2); Galena (PbS) Chalcopyrite (CuFeS2); Magnetite (Fe3O4) Galena (PbS); Wolframite ((Mn,Fe)WO4); Scheelite (CaWO4) Barium sulphate (BaSO4); Sphalerite (ZnS); Galena (PbS) Chalcopyrite (CuFeS2); Galena (PbS) Galena (PbS); Chalcopyrite (CuFeS2); Barium sulphate (BaSO4); Sphalerite (ZnS) Hematite (Fe2O3) Hematite (Fe2O3) Graphite (C) Galena (PbS); Barium sulphate (BaSO4); Fluorite (CaF2) Galena (PbS) Coal Galena (PbS); Baryte (BaSO4); Cerussite (PbCO3); Aragonite (CaCO3) Slate Galena (PbS); Sphalerite (ZnS) Chalcopyrite (CuFeS2) Primary Metal Pollutants Copper (Cu); Lead (Pb) Copper (Cu); Iron (Fe) Lead (Pb) Tungsten (W) Zinc (Zn); Lead (Pb); Silver (Ag) Lead (Pb); Copper (Cu) Lead (Pb); Copper (Cu); Zinc (Zn); Silver (Ag) Iron (Fe) Iron (Fe) N/A Lead (Pb); Lead (Pb) N/A Lead (Pb);

NY328352

8 9 10 11 12 13 14

NY018103 SD174791 NY231128 NY763227 NY784434 NX967176 NY232222

Hodbarrow Mine Seathwaite Graphite Mine Hilton Mine Nenthead Mine

Haig Pit Barrow and Uzzicar Mine Penny Rigg Quarry Myers Head Mine Greenburn Mine

15 16 17

NY306008 NY395119 NY290022

N/A Lead (Pb); Zinc (Zn) Copper (Cu)

111

1. 2. 3. 4. 5. 6. 7. 8. 9.

Goldscope Mine Coniston Copper Mine Greenside Lead Mine Carrock Mine Force Crag Mine Roughton Gill Mine Driggeth Mine Florence Mine Hodbarrow Mine

12. Nenthead Mine 13. Haig Pit 14. Barrow and Uzzicar Mine 15. Penny Rigg Quarry 16. Myers Head Mine 17. Greenburn Mine

10. Seathwaite Mine 11. Hilton Mine 112

8 APPENDIX 2: INVENTORY OF EQUIPMENT USED

Equipment JMC Backsaver N2 Handle Purpose Facilitates the penetration of attachable sampling tubes through the soil/sediment Collect increments in wet soil/sediment Miscellaneous Part Number: PN001 Part Number: PN006 Core diameter: 0.688 in (1.748 cm); Core length: 12 in (30.48 cm); Sample length: 9 in (22.86 cm) JMC Dry Sampling Tube Collect increments in dry soil/sediment Part Number: PN007 Core diameter: 0.750 in (1.905 cm); Core length: 12 in (30.48 cm); Sample length: 9 in (22.86 cm) JMC Special Cleaner To retrieve samples and clean sampling tube To attach and remove the sampling tubes To record waypoints of each sampling site for GIS analysis and map producing Storage of composite samples. 30 per marsh equals a total of 60 composite samples. 20 spare bags in case of damage. To reduce contamination between sites. To keep composite samples cool and reduce the volatility of their constituents. Construct maps of study area; create interpolation maps of the concentrations of heavy-metals in each saltmarsh -

JMC Wet Sampling Tube

Adjustable spanner Garmin GPS62 GPS device

80 (203mm x 279mm x 50my) polythene storage bags 10 pairs of nitric gloves 1 Thermos cool bag

ESRI ArcMap 10.0 software

Hanna Combo HI98129 pH/EC/TDS meter

113

9 APPENDIX 3: RAW PRIMARY DATA

9.1 Plumpton Marsh 9.1.1 pH and Electrical Conductivity (Siemens/cm)
SITE_ID Weight_in_Bag Bag_Weight Sample_weight Half_Weight PH1 PH2 PH3 PH_MEAN EC1 EC2 EC3 EC_MEAN 1 541.86 5.9 535.96 267.98 8.95 8.95 8.88 8.93 650 705 702 686 2 564.30 5.9 558.40 279.20 9.03 8.98 8.82 8.94 698 722 724 715 3 475.84 5.9 469.94 234.97 8.38 8.26 8.25 8.30 586 621 627 611 4 541.24 5.9 535.34 267.67 8.97 8.83 8.39 8.73 448 529 560 512 5 514.50 5.9 508.60 254.30 8.33 8.27 8.29 8.30 722 753 812 762 6 528.95 5.9 523.05 261.53 9.05 8.75 9.05 8.95 343 345 366 351 7 542.17 5.9 536.27 268.14 9.10 8.93 9.06 9.03 397 416 418 410 8 531.44 5.9 525.54 262.77 8.11 7.81 8.15 8.02 862 960 963 928 9 379.01 5.9 373.11 186.56 8.49 8.40 8.72 8.54 637 642 663 647 10 543.54 5.9 537.64 268.82 8.55 8.84 8.90 8.76 371 373 384 376 11 617.77 5.9 611.87 305.94 8.83 8.88 8.76 8.82 1157 1224 1230 1204 12 559.14 5.9 553.24 276.62 8.61 9.07 8.61 8.76 584 576 638 599 13 572.10 5.9 566.20 283.10 8.48 9.03 9.04 8.85 509 544 554 536 14 554.07 5.9 548.17 274.09 8.99 8.57 8.46 8.67 488 503 525 505 15 561.75 5.9 555.85 277.93 8.61 8.64 8.71 8.65 510 543 538 530 16 505.88 5.9 499.98 249.99 7.86 7.77 8.27 7.97 561 613 585 586 17 479.59 5.9 473.69 236.85 8.77 8.71 8.78 8.75 419 422 441 427 18 364.34 5.9 358.44 179.22 8.09 7.88 7.59 7.85 583 587 626 599 19 507.11 5.9 501.21 250.61 8.20 8.24 8.16 8.20 457 467 489 471 20 523.12 5.9 517.22 258.61 9.07 9.14 9.63 9.28 524 588 601 571 21 577.04 5.9 571.14 285.57 9.02 9.36 8.78 9.05 398 408 509 438 22 533.53 5.9 527.63 263.82 8.97 8.94 8.89 8.93 346 358 365 356 23 524.64 5.9 518.74 259.37 8.98 8.69 8.72 8.80 650 659 667 659 24 485.76 5.9 479.86 239.93 8.42 8.74 8.71 8.62 748 733 853 778 25 498.16 5.9 492.26 246.13 8.46 7.99 8.12 8.19 587 740 775 701 26 433.86 5.9 427.96 213.98 8.04 8.57 8.62 8.41 960 1085 1098 1048 27 535.76 5.9 529.86 264.93 8.96 8.58 8.61 8.72 598 720 731 683 28 539.23 5.9 533.33 266.67 8.97 8.94 8.65 8.85 753 751 746 750 29 572.39 5.9 566.49 283.25 8.42 8.73 8.94 8.70 613 679 710 667 30 422.00 5.9 416.10 208.05 7.48 7.56 7.35 7.46 284 281 290 285

114

9.1.2 Moisture Content (%) and Loss On Ignition (%)

SITE_ID CW1 WSW1 TW1 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 19.69 15.62 20.15 18.95 19.29 18.82 19.92 20.31 18.69 35.39 11.69 58.43 56.59 35.60 34.03 10.00 10.01 10.01 10.00 10.00 9.99 10.01 10.01 9.99 9.99 9.99 10.00 10.00 10.00 10.00 29.69 25.62 30.16 28.96 29.28 28.81 29.93 30.32 28.68 45.38 21.68 68.43 66.59 45.60 44.03 TD1 DSW1 MC1 27.19 22.46 26.78 26.65 25.93 26.20 27.56 27.35 25.87 42.31 19.01 66.15 63.41 42.95 41.86 7.50 6.84 6.63 7.69 6.64 7.39 7.64 7.04 7.18 6.92 7.32 7.72 6.82 7.35 7.83 24.98 31.61 33.76 23.11 33.57 26.10 23.61 29.67 28.17 30.77 26.73 22.83 31.75 26.47 21.77 AS1 SOM1 CW2 WSW2 TW2 26.79 22.08 26.36 26.30 25.47 25.76 27.14 27.00 25.50 41.96 18.75 65.98 63.12 42.75 41.74 5.32 5.60 6.27 4.56 6.96 6.04 5.56 4.93 5.15 5.01 3.54 2.16 4.33 2.79 1.44 18.46 19.04 18.69 19.87 20.13 15.62 16.95 18.55 20.02 20.00 20.74 18.60 20.38 18.69 20.15 9.99 10.00 9.99 10.00 10.00 10.00 10.01 10.01 10.00 9.99 9.99 10.00 10.00 10.01 10.01 28.45 29.04 28.69 29.87 30.13 25.62 26.96 28.56 30.02 29.99 30.73 28.61 30.37 28.70 30.16 TD2 25.66 25.89 25.49 27.57 27.02 23.40 24.64 25.11 26.98 27.17 28.22 26.36 27.34 26.11 27.83 DSW2 MC2 7.20 6.85 6.80 7.70 6.89 7.78 7.70 6.56 6.96 7.17 7.48 7.76 6.97 7.42 7.68 27.92 31.49 31.93 23.00 31.09 22.20 23.14 34.48 30.36 28.24 25.18 22.48 30.31 25.86 23.25 AS2 25.46 25.54 25.12 27.38 26.57 23.08 24.36 24.66 26.26 26.85 27.98 26.14 27.03 25.87 27.70 SOM2 CW3 WSW3 TW3 2.78 5.17 5.56 2.40 6.55 4.14 3.65 6.79 10.40 4.51 3.17 2.83 4.50 3.23 1.74 15.87 17.23 16.12 18.82 19.21 18.96 41.85 16.21 35.72 34.65 17.75 20.02 20.38 34.31 34.55 10.00 10.00 9.99 10.00 10.00 10.00 10.01 10.00 10.01 10.00 9.99 9.99 10.01 10.00 10.00 25.87 27.23 26.11 28.82 29.22 28.96 51.86 26.22 45.73 44.65 27.74 30.01 30.38 44.31 44.55 TD3 23.32 24.24 22.17 26.51 26.14 26.51 49.19 23.31 43.13 41.83 25.01 27.82 27.13 41.64 42.25 DSW3 MC3 7.46 7.01 6.05 7.69 6.92 7.55 7.34 7.10 7.41 7.18 7.26 7.80 6.75 7.34 7.71 25.45 29.94 39.46 23.15 30.78 24.52 26.62 29.05 25.96 28.17 27.32 21.98 32.53 26.65 22.97 AS3 22.90 23.90 21.63 26.15 25.66 26.04 48.84 22.95 42.83 41.48 24.55 27.41 26.75 41.24 41.87 SOM3 MCM MCS SOMM SOMS 5.73 4.77 8.95 4.64 6.95 6.14 4.81 5.12 4.02 4.86 6.30 5.19 5.56 5.47 5.04 26.12 31.01 35.05 23.09 31.81 24.27 24.46 31.07 28.17 29.06 26.41 22.43 31.53 26.33 22.66 1.58 0.93 3.93 0.08 1.53 1.96 1.89 2.98 2.20 1.48 1.10 0.43 1.13 0.41 0.79 4.61 5.18 6.93 3.86 6.82 5.44 4.67 5.61 6.52 4.80 4.34 3.39 4.80 3.83 2.74 1.59 0.41 1.79 1.27 0.23 1.13 0.96 1.03 3.40 0.26 1.71 1.59 0.66 1.44 1.99

KEY: CW = Crucible Weight (g); WSW = Wet Sample Weight (g); TW = Total Weight (g); TD = Total Dry (g); DSW = Dry Sample Weight (g); MC = Moisture Content (%); AS = Ashed Sample (g); SOM = Soil Organic Matter (%); MCM = Moisture Content Mean (%); MCS = Moisture Content Standard Deviation; SOMM = Soil Organic Matter Mean (%); SOMS = Soil Organic Matter Standard Deviation

115

9.2 Plumpton Hall 9.2.1 pH and Electrical Conductivity (Siemens cm-1)

SITE_ID 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 Weight_in_Bag 315.84 406.94 627.80 496.14 223.28 541.32 355.17 221.39 486.34 223.98 502.16 398.27 433.86 588.44 624.52 614.94 583.22 597.76 395.37 637.97 541.21 284.42 458.51 383.64 553.17 184.05 473.43 584.24 239.57 383.89 Bag_Weight 5.90 5.90 5.90 5.90 5.90 5.90 5.90 5.90 5.90 5.90 5.90 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 7.84 Sample_weight 309.94 401.04 621.90 490.24 217.38 535.42 349.27 215.49 480.44 218.08 496.26 390.43 426.02 580.60 616.68 607.10 575.38 589.92 387.53 630.13 533.37 276.58 450.67 375.80 545.33 176.21 465.59 576.40 231.73 376.05 Half_Weight 154.97 200.52 310.95 245.12 108.69 267.71 174.64 107.75 240.22 109.04 248.13 195.22 213.01 290.30 308.34 303.55 287.69 294.96 193.77 315.07 266.69 138.29 225.34 187.90 272.67 88.11 232.80 288.20 115.87 188.03 PH1 8.07 8.35 9.01 8.24 8.40 8.07 8.87 7.89 8.38 7.65 7.57 7.83 8.06 9.08 8.71 9.08 9.16 9.09 8.29 9.18 8.61 7.73 8.30 8.29 8.86 8.06 8.02 8.96 8.25 7.81 PH2 8.45 8.39 8.50 8.65 8.11 8.21 8.44 8.27 8.35 8.03 7.91 7.71 8.57 9.21 8.66 9.10 8.75 8.62 8.45 9.01 8.34 7.76 8.66 8.62 8.44 8.07 8.32 8.54 8.31 7.75 PH3 8.43 8.02 8.85 8.68 8.49 8.65 8.48 8.27 8.73 7.70 8.21 7.77 8.53 8.79 9.04 8.74 9.09 9.01 8.19 9.03 8.37 8.04 8.69 8.53 8.74 8.04 8.31 8.54 8.02 8.07 PH_MEAN 8.32 8.25 8.79 8.52 8.33 8.31 8.60 8.14 8.49 7.79 7.90 7.77 8.39 9.03 8.80 8.97 9.00 8.91 8.31 9.07 8.44 7.84 8.55 8.48 8.68 8.06 8.22 8.68 8.19 7.88 EC1 1376 1021 929 864 463 875 1169 1001 890 1429 571 113 1037 702 1062 871 869 663 911 680 754 1237 1241 1314 944 422 1124 1212 443 1150 EC2 1491 1433 995 900 490 1018 1195 1060 925 1504 644 134 1150 725 1056 887 852 770 1054 744 795 1291 1330 1379 933 426 1145 1192 452 1166 EC3 1501 1500 1002 911 518 1072 1187 1051 950 1549 661 134 1172 712 1062 864 871 797 1034 756 810 1520 1348 1381 952 429 1153 1188 457 1205 EC_MEAN 1456 1318 975 892 490 988 1184 1037 922 1494 625 127 1120 713 1060 874 864 743 1000 727 786 1349 1306 1358 943 426 1141 1197 451 1174

116

SITE_ID Weight_in_Bag Bag_Weight Sample_weight Half_Weight PH1 PH2 PH3 PH_MEAN EC1 EC2 EC3 EC_MEAN 1 315.84 5.90 309.94 154.9700 8.07 8.45 8.43 8.32 1376 1491 1501 1456 2 406.94 5.90 401.04 200.5200 8.35 8.39 8.02 8.25 1021 1433 1500 1318 3 627.80 5.90 621.90 310.9500 9.01 8.50 8.85 8.79 929 995 1002 975 4 496.14 5.90 490.24 245.1200 8.24 8.65 8.68 8.52 864 900 911 892 5 223.28 5.90 217.38 108.6900 8.40 8.11 8.49 8.33 463 490 518 490 6 541.32 5.90 535.42 267.7100 8.07 8.21 8.65 8.31 875 1018 1072 988 7 355.17 5.90 349.27 174.6350 8.87 8.44 8.48 8.60 1169 1195 1187 1184 8 221.39 5.90 215.49 107.7450 7.89 8.27 8.27 8.14 1001 1060 1051 1037 9 486.34 5.90 480.44 240.2200 8.38 8.35 8.73 8.49 890 925 950 922 10 223.98 5.90 218.08 109.0400 7.65 8.03 7.70 7.79 1429 1504 1549 1494 11 502.16 5.90 496.26 248.1300 7.57 7.91 8.21 7.90 571 644 661 625 12 398.27 7.84 390.43 195.2150 7.83 7.71 7.77 7.77 113 134 134 127 13 433.86 7.84 426.02 213.0100 8.06 8.57 8.53 8.39 1037 1150 1172 1120 14 588.44 7.84 580.60 290.3000 9.08 9.21 8.79 9.03 702 725 712 713 15 624.52 7.84 616.68 308.3400 8.71 8.66 9.04 8.80 1062 1056 1062 1060 16 614.94 7.84 607.10 303.5500 9.08 9.10 8.74 8.97 871 887 864 874 17 583.22 7.84 575.38 287.6900 9.16 8.75 9.09 9.00 869 852 871 864 18 597.76 7.84 589.92 294.9600 9.09 8.62 9.01 8.91 663 770 797 743 19 395.37 7.84 387.53 193.7650 8.29 8.45 8.19 8.31 911 1054 1034 1000 20 637.97 7.84 630.13 315.0650 9.18 9.01 9.03 9.07 680 744 756 727 21 541.21 7.84 533.37 266.6850 8.61 8.34 8.37 8.44 754 795 810 786 22 284.42 7.84 276.58 138.2900 7.73 7.76 8.04 7.84 1237 1291 1520 1349 23 458.51 7.84 450.67 225.3350 8.30 8.66 8.69 8.55 1241 1330 1348 1306 24 383.64 7.84 375.80 187.9000 8.29 8.62 8.53 8.48 1314 1379 1381 1358 25 553.17 7.84 545.33 272.6650 8.86 8.44 8.74 8.68 944 933 952 943 26 184.05 7.84 176.21 88.1050 8.06 8.07 8.04 8.06 422 426 429 426 27 473.43 7.84 465.59 232.7950 8.02 8.32 8.31 8.22 1124 1145 1153 1141 28 584.24 7.84 576.40 288.2000 8.96 8.54 8.54 8.68 1212 1192 1188 1197 29 239.57 7.84 231.73 115.8650 8.25 8.31 8.02 8.19 443 452 457 451 30 383.89 7.84 376.05 188.0250 7.81 7.75 8.07 7.88 1150 1166 1205 1174

117

9.2.2 Moisture Content (%) and Loss On Ignition (%)

SITE_ID CW1 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 SITE_ID 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 34.31 34.31 33.65 35.80 34.50 36.03 33.86 34.99 32.32 36.43 35.56 35.87 34.44 34.55 34.96 WSW1 9.99 10.01 10.02 10.01 10.04 10.01 10.00 10.00 10.00 9.99 10.01 10.02 9.99 10.00 10.00 WSW1 9.99 10.01 10.02 10.01 10.04 10.01 10.00 10.00 10.00 9.99 10.01 10.02 9.99 10.00 10.00 TW1 44.30 44.32 43.66 45.81 44.54 46.04 43.86 44.99 42.33 46.42 45.56 45.89 44.43 44.55 44.96 TW1 44.30 44.32 43.66 45.81 44.54 46.04 43.86 44.99 42.33 46.42 45.56 45.89 44.43 44.55 44.96 TD1 40.40 41.57 37.45 42.41 41.68 42.34 39.94 42.66 40.13 42.91 42.52 41.89 41.88 40.35 40.33 TD1 DSW1 MC1 AS1 SOM1 5.18 2.88 11.11 5.19 3.11 5.68 6.18 2.84 2.16 5.16 3.92 6.10 3.38 8.82 7.87 WSW2 10.00 10.06 10.00 10.01 10.04 10.03 10.05 10.03 10.01 10.04 10.03 10.00 10.00 10.01 10.01 CW2 WSW2 TW2 TD2 22.15 28.20 15.68 26.33 26.47 26.36 26.77 26.88 27.76 27.73 28.05 40.76 40.04 41.40 26.49 AS2 21.69 27.82 15.12 25.89 26.05 26.02 26.31 26.50 27.38 27.24 27.64 40.25 39.66 40.84 26.00 DSW2 6.11 7.41 3.99 6.64 7.00 6.44 6.46 7.59 7.86 6.57 6.89 6.07 7.53 6.01 5.50 SOM2 7.55 5.19 14.07 6.59 5.99 5.32 7.24 5.11 4.76 7.39 5.90 8.53 5.00 9.33 8.91 MC2 AS2 SOM2 CW3 20.13 15.61 18.46 20.05 18.54 20.15 19.04 18.62 20.73 34.99 34.95 34.31 35.80 34.43 35.56 DSW3 6.12 7.41 4.28 6.45 7.00 6.39 7.56 6.31 7.83 6.84 6.63 5.78 7.62 5.33 5.41 WSW3 TW3 TD3 26.24 23.02 22.74 26.50 25.54 26.54 26.60 24.93 28.56 41.83 41.59 40.09 43.42 39.75 40.97 MCM 38.96 26.57 59.80 34.46 29.59 36.32 33.15 28.16 21.73 33.78 31.77 40.45 24.65 42.90 45.77 DSW3 MC3 AS3 SOM3 7.67 5.09 13.05 7.50 5.94 5.64 3.09 5.93 5.03 6.52 5.59 9.36 5.18 11.44 9.07 MCM 38.96 26.57 59.80 34.46 29.59 36.32 33.15 28.16 21.73 33.78 31.77 40.45 24.65 42.90 45.77 40.40 6.09 39.01 40.08 41.57 7.26 27.48 41.36 37.45 3.80 62.03 37.03 42.41 6.61 33.99 42.07 41.68 7.18 28.50 41.46 42.34 6.31 37.01 41.98 39.94 6.08 39.25 39.56 42.66 7.66 23.33 42.44 40.13 7.81 21.93 39.96 42.91 6.47 35.22 42.57 42.52 6.97 30.39 42.25 41.89 6.02 39.92 41.52 41.88 7.44 25.52 41.63 40.35 5.80 42.01 39.84 40.33 5.37 46.28 39.91 DSW1 MC1 AS1 SOM1 CW2 6.09 39.01 40.08 5.18 16.05 7.26 27.48 41.36 2.88 20.79 3.80 62.03 37.03 11.11 11.69 6.61 33.99 42.07 5.19 19.69 7.18 28.50 41.46 3.11 19.48 6.31 37.01 41.98 5.68 19.92 6.08 39.25 39.56 6.18 20.31 7.66 23.33 42.44 2.84 19.29 7.81 21.93 39.96 2.16 19.90 6.47 35.22 42.57 5.16 21.16 6.97 30.39 42.25 3.92 21.15 6.02 39.92 41.52 6.10 34.69 7.44 25.52 41.63 3.38 32.51 5.80 42.01 39.84 8.82 35.39 5.37 46.28 39.91 7.87 20.99 16.05 10.00 26.05 20.79 10.06 30.85 11.69 10.00 21.69 19.69 10.01 29.70 19.48 10.04 29.52 19.92 10.03 29.95 20.31 10.05 30.37 19.29 10.03 29.32 19.90 10.01 29.91 21.16 10.04 31.20 21.15 10.03 31.18 34.69 10.00 44.70 32.51 10.00 42.51 35.39 10.01 45.40 20.99 10.01 31.00 TW2 TD2 DSW2 MC2 26.05 22.15 6.11 38.91 30.85 28.20 7.41 26.32 21.69 15.68 3.99 60.09 29.70 26.33 6.64 33.68 29.52 26.47 7.00 30.32 29.95 26.36 6.44 35.79 30.37 26.77 6.46 35.76 29.32 26.88 7.59 24.25 29.91 27.76 7.86 21.49 31.20 27.73 6.57 34.54 31.18 28.05 6.89 31.25 44.70 40.76 6.07 39.31 42.51 40.04 7.53 24.73 45.40 41.40 6.01 39.92 31.00 26.49 5.50 45.06 38.91 21.69 7.55 26.32 27.82 5.19 60.09 15.12 14.07 33.68 25.89 6.59 30.32 26.05 5.99 35.79 26.02 5.32 35.76 26.31 7.24 24.25 26.50 5.11 21.49 27.38 4.76 34.54 27.24 7.39 31.25 27.64 5.90 39.31 40.25 8.53 24.73 39.66 5.00 39.92 40.84 9.33 45.06 26.00 8.91 CW3 WSW3 TW3 TD3 20.13 10.02 30.15 26.24 15.61 10.00 25.61 23.02 18.46 10.03 28.48 22.74 20.05 10.04 30.08 26.50 18.54 9.99 28.53 25.54 20.15 10.00 30.15 26.54 19.04 10.00 29.04 26.60 18.62 10.01 28.62 24.93 20.73 10.01 30.74 28.56 34.99 10.00 44.99 41.83 34.95 10.00 44.95 41.59 34.31 9.99 44.30 40.09 35.80 9.99 45.79 43.42 34.43 10.01 44.43 39.75 35.56 10.01 45.58 40.97 10.02 30.15 10.00 25.61 10.03 28.48 10.04 30.08 9.99 28.53 10.00 30.15 10.00 29.04 10.01 28.62 10.01 30.74 10.00 44.99 10.00 44.95 9.99 44.30 9.99 45.79 10.01 44.43 10.01 45.58 MC3 AS3 SOM3 38.95 25.77 7.67 25.90 22.65 5.09 57.29 22.18 13.05 35.71 26.01 7.50 29.94 25.12 5.94 36.16 26.18 5.64 24.42 26.36 3.09 36.89 24.56 5.93 21.78 28.17 5.03 31.59 41.38 6.52 33.68 41.22 5.59 42.11 39.55 9.36 23.69 43.03 5.18 46.75 39.15 11.44 45.98 40.48 9.07 6.12 38.95 25.77 7.41 25.90 22.65 4.28 57.29 22.18 6.45 35.71 26.01 7.00 29.94 25.12 6.39 36.16 26.18 7.56 24.42 26.36 6.31 36.89 24.56 7.83 21.78 28.17 6.84 31.59 41.38 6.63 33.68 41.22 5.78 42.11 39.55 7.62 23.69 43.03 5.33 46.75 39.15 5.41 45.98 40.48 MCS SOMM SOMS 0.05 6.80 1.41 0.82 4.39 1.31 2.38 12.74 1.50 1.09 6.43 1.16 0.96 5.01 1.65 0.62 5.54 0.20 7.75 5.50 2.15 7.57 4.62 1.60 0.23 3.98 1.59 1.93 6.35 1.12 1.71 5.14 1.06 1.47 8.00 1.70 0.92 4.52 0.99 3.50 9.87 1.39 0.64 8.62 0.65

CW1 34.31 34.31 33.65 35.80 34.50 36.03 33.86 34.99 32.32 36.43 35.56 35.87 34.44 34.55 34.96

118

KEY: CW = Crucible Weight (g); WSW = Wet Sample Weight (g); TW = Total Weight (g); TD = Total Dry (g); DSW = Dry Sample Weight (g); MC = Moisture Content (%); AS = Ashed Sample (g); SOM = Soil Organic Matter (%); MCM = Moisture Content Mean (%); MCS = Moisture Content Standard Deviation; SOMM = Soil Organic Matter Mean (%); SOMS = Soil Organic Matter Standard Deviation

119