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Port Pirie Phase 1 Project MEASURING, MODELLING AND MANAGING LEGACIES OF MARINE POLLUTION AS

NEW RESOURCES

Dr. Hazel Vandeleur | PG101341-343 | 27/07/2020

South Australia

~ University of

South Australia

Flinders~ Ports ~

nJrstar

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Contents

Summary ...................................................................................................................................................

1 Introduction .................................................................................................................................... 1

2 Method ........................................................................................................................................... 4

2.1 Study site ................................................................................................................................. 4

2.2 Field work ................................................................................................................................ 4

2.2.1 Water quality sampling ................................................................................................... 5

2.2.2 Sediment sampling .......................................................................................................... 5

2.3 Study limitations ................................................................................................................... 10

2.4 Laboratory analyses .............................................................................................................. 11

2.4.1 Particle size analysis ...................................................................................................... 11

2.4.2 Carbon/Nitrogen/Sulphur (CNS) estimation ................................................................. 11

2.4.3 Total metal concentration ............................................................................................ 11

2.4.4 Spatial analysis .............................................................................................................. 12

2.4.5 Resource estimation ..................................................................................................... 12

3 Results ........................................................................................................................................... 13

3.1 Water quality ........................................................................................................................ 13

3.2 Sediment Quality................................................................................................................... 16

3.2.1 Historic metal concentrations ....................................................................................... 16

3.2.2 Particle size analysis ...................................................................................................... 18

3.2.3 Surface metal concentrations ....................................................................................... 18

3.2.4 Metal concentrations in deeper layers (shallow waters only) ...................................... 24

3.2.5 Metal concentrations in size fractions (limited study) ................................................. 25

5 Potential asset recovery value ...................................................................................................... 30

5.1 Alignment with maintenance dredging requirements. ........................................................ 33

6 Discussion ...................................................................................................................................... 35

7 Conclusion ..................................................................................................................................... 40

7.1 Way forward ......................................................................................................................... 40

8 References .................................................................................................................................... 42

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Figure 1 - Project field work and testing details ..................................................................................... 4

Figure 2 - Sediment sampling sites (‘C’ indicates deeper core samples were taken). Port Davis (Site

20.0C) and Fisherman’s Bay (Site 19.0C) were included as ‘background’ comparison sites. ................. 6

Figure 3 - Sediment sampling sites (‘C’ indicates deeper core samples were taken) excluding

background sites. Sites Samph 1-6 are additional terrestrial sites in samphire habitat. ....................... 7

Figure 4 - Sediment sampling sites within Port Pirie river (‘C’ indicates deeper core samples were

taken). ..................................................................................................................................................... 8

Figure 5 - Water sampling sites within Germein Bay. An additional sample (5.1) was taken at site 5 in

the prop wash of an ore vessel leaving Port. .......................................................................................... 9

Figure 6 -Historic dredge disposal areas (approximate locations from Wagstaff 1983) with current

sediment site locations. ........................................................................................................................ 17

Figure 7 - Map of dissimilarity for a 2-dimensional representation in space for individual metal

concentrations in Port Pirie surface sediments. ................................................................................... 19

Figure 8 - Zones as grouped by metal concentrations where red = high metal contamination (most

sites over GV-high for 2 or more metals), amber = intermediate metal contamination (most sites

with one or more metal over GV-low) and green = low contamination levels (few sites with GV

exceedances)......................................................................................................................................... 22

Figure 9 - Proportion of each sediment size fraction for site divided into sub-fractions for metal

analysis .................................................................................................................................................. 25

Figure 10 - Potential First Creek and Port Pirie river asset recovery areas .......................................... 31

Figure 11 - Maintenance dredging area requirements for shipping channel to gazetted navigational

depth as identified by Flinders Ports (2020) ......................................................................................... 34

0

Table 1 - Temperature, salinity, pH and chlorophyll levels at study sites ............................................ 13

Table 2 - Proximity matrix (Pearson correlation coefficient) for individual metals in Port Pirie surface

sediments. ............................................................................................................................................. 19

Table 3 - Metal concentrations within size fractions of sub-section of Port Pirie surface sediment

samples ................................................................................................................................................. 29

Table 4 - Mean, standard deviation, maximum and minimum values for As, Pb and Zn within the Port

Pirie river and First Creek asset recovery areas. ................................................................................... 30

Table 5 – Potential asset recovery calculations for Pb and Zn ............................................................. 32

Table 6 - Potential asset recovery calculations for Ag *Calculated as 5% of the Port Pirie metal

recovery area due to its restricted distribution alongside the Smelter berths. ................................... 32

Table 7 - Maintenance dredging requirements by area and volume as supplied by Flinders Ports

(2020). ................................................................................................................................................... 33

Table 8 – Maximum metal concentrations (mg/kg) in surface sediments from industrial and urban

marine and coastal systems. ................................................................................................................. 36

Appendix table A- Site number, date sampled, location and site description including main habitat

type. ...................................................................................................................................................... 52

Appendix table B - Metal concentration results in water samples ....................................................... 54

Appendix table C - Metal concentrations, CNS percentages and PSA in surface sediment samples at

Port Pirie. Note: CNS and PSA only undertaken on sample 1-65. ....................................................... 58

Appendix table D - Metal concentrations within core sediment samples (core 1.0 – 22.0C) at Port

Pirie. ...................................................................................................................................................... 68

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PROJECT DETAILS

Project Number: PG101341-343

Project Title: Measuring, monitoring and managing legacies of marine pollution as new

resources

Project Industry Partners – Flinders Ports, Nyrstar Port Pirie and South Australian EPA

Report Author: Dr Hazel Vandeleur

Note: This document was produced as an electronic document. Supporting files (PDF’s 1-14) are

provided separately along with instructions for use of their ‘clickable’ feature layers.

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Summary

The Port Pirie metals recovery project, undertaken by a collaborative partnership team of UniSA,

Flinders Ports, Nyrstar Port Pirie and the SA EPA, examined the potential for metal recovery from

contaminated sediments at Port Pirie.

New mapping and analysis of the shallow sediments and overlying waters at Port Pirie demonstrated

that 130 years of industrial smelting and refining of metals at Port Pirie have resulted in some of the

highest concentrations of Pb, Zn and Cd recorded in the marine environment. Results demonstrate

that the metal contamination levels can be classified into spatial zones of high (Zone 1),

intermediate (Zone 2) and low (Zone 3) level contamination. Zone 1 (approx. 10 x 10 km2) was

significantly impacted with Pb, Zn and Cd levels in sediment up to 50 times higher than the

ANZECC/ARMCANZ sediment guidelines values (SQGV), with many sites indicating that toxicity

would be expected on organisms inhabiting the sediments. Further, the overlying water metal

concentrations of Zn at every site tested exceeded the 95% ANZECC/ARMCANZ species protection

levels with most sites within Zone 1 exceeding the Species Protection Level’s (SPL’s) for multiple

metals. Zone 2 reported largely intermediate sediment metal concentrations where most sites and

metals (Pb, Zn, Cd,) had exceedances over the SQGV-low values but below SQGV-high values. Zone 3

reported few exceedances over guideline values and the sites can be considered as non-

contaminated but still above what might be considered background.

Sediments provide the foundation blocks of many marine food webs and the health of sediments

have direct bearing on the health of the systems they support. High metal concentrations in

sediments have been shown to have toxic effects on individual species, which in turn drives

community and ecosystem impacts. Metal contamination decreases species diversity, changes

community structure, results in abundance and biomass decline and degrades habitats.

Consequential effects can include reductions in both marine resource yields and ecosystem services.

Over time the Port Pirie Harbor has accumulated silt resulting in restrictions to shipping around

tides. The high level of metal contamination has resulted in dredge spoil disposal being cost

prohibitive and reduced efficiency of shipping has been ongoing. This issue has also inhibited

development of the Port, reduced recreational fishing and tourism opportunities in the local area.

Further to this, Port Pirie is now overlooked for prospective development (e.g. iron ore export)

requiring expensive and damaging development of new ports in undeveloped areas of our coast. A

lack of solutions for the contaminated sediments has resulted in little substantive removal of

contaminated material thereby fuelling the status quo.

We provide an alternative solution whereby the metals contaminating the environment are

reimagined as assets. Conservative initial estimates of recovered metal value in restricted areas

within Zone 1 (the Port Pirie river and First Creek) are between $21.5 and $40 million in Pb, Zn and

Ag alone. The estimates are conservative, and the areas targeted are those most significantly

impacted ecologically. Removal of these sediments will recover approx 3200 tonnes of Pb and 4500

tonnes of Zn, thereby significantly reduce the metal loading within the sites. The recovered metal

value can thereby offset remediation costs, resulting in a slow but ongoing recovery of ecosystem

services. This also provides added benefits to Nyrstar of opportunities for recovering social licence

from the Port Pirie and regional communities after years of issues due to air quality.

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The implementation of the asset recovery project to ‘Proof of concept’ could be a win-win for the

environment and the city of Port Pirie. Recovering metals from contaminated matrices could cost-

effectively remediate impacted marine environments and open the Port for potential expansion into

the future. Key to future stages is the confirmation of metal concentrations in the deeper sediments

and waters of the shipping channel, and the exploration of existing technologies, thereby

streamlining costs, available for processing and concentration of the sediments.

Many of our coastal and marine environments bear the legacy of our industrial past with extremely

high levels of metal contamination within the sediments and associated flora and fauna. Ultimately,

the degraded and contaminated status of the Port Pirie marine environment will not change without

action. Currently the potential for diversification of Port Pirie from a smelter focused city to a multi-

user Port with industrial, recreational and tourism interests is limited by the high levels of

contamination. Altering the way that contaminated systems are managed and re-imagining the

contamination as an asset recovery has the potential to encourage the clean-up of pollution legacies

leading to better outcomes, more efficient industry practices and new opportunities.

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1 Introduction

Since commencing operations in 1889, the Port Pirie smelter has grown to be one of the world’s

largest primary lead smelting facilities. However, a 130 year legacy of ineffective emission control

has resulted in significantly high levels of metals in the marine environment, particularly within the

sediments (Dossis and Warren 1981, Ward and Young 1981; Ward and Young 1982, Ward and Young

1983; Ward 1984, Norrish et al. 1986, Ward and Hutchings 1986, Ward 1987, Tiller et al. 1989).

Many of the metals reported are considered amongst the most toxic contaminants currently

threatening human health (McCartor and Becker 2010).

Remediation of metal contaminated sediments at sites such as Port Pirie is difficult and expensive,

and no remediation has been undertaken outside of disposal from small-scale dredging of boat

ramps and berth pockets. Reimagining these metal contaminated sediments as potential asset

repositories could fundamentally change how we manage and remediate polluted systems.

Moreover, altering the way that contaminated systems are dealt with will encourage the clean-up of

pollution legacies leading to better outcomes, more efficient industry practices and new

opportunities.

The Spencer Gulf is an inverse estuary with high salinity in the range of 42-47 parts per thousand

(‰) at the head of the Gulf decreasing towards the mouth (Nunes Vaz et al. 1990). This is largely due

to limited freshwater and evaporation amounts being nearly equal to the yearly rainfall amount

(Australian Bureau of Meteorology 2016). Port Pirie sits within Germein Bay on the eastern shore of

Spencer Gulf, 223km north of Adelaide. It sits within a typical temperate system with fringing

mangroves grading inshore to saltmarsh habitats and extending seaward to mud and sandflats with

seagrass growing from the intertidal down to approx. 12m subtidally (Edyvane 1999). The marine

environment of Port Pirie is generally shallow and less than 8m particularly around Port Pirie

although there are limited deeper areas and the shipping channel itself has a max of ~15m deep.

The Port Pirie marine and coastal environment receives inputs both directly and indirectly from the

smelter. As well as receiving Pb contaminated airborne particulate matter, effluent has been

discharged to the marine environment adjacent to the smelter since 1889 with metal–rich effluent

discharged into First Creek since 1939 (and into Port Pirie River for fifty years prior to that). Other

pathways for metals into the marine environment include spillage and fugitive dust emissions at the

wharf during ship loading, direct atmospheric deposition to marine waters, and indirect deposition

via contaminated groundwater flows and storm water runoff, which drain largely into Port Pirie

River (Gaylard 2014). The smelter straddles a drainage divide with parts of the westernmost portion

draining to the Spencer Gulf. Surface waters of the site (including dust suppression waters) drain

into a stormwater drainage system and then into the smelter sedimentation pond and into First

Creek. However, rainfall in the western unpaved areas of the main operational smelter (including the

interim storage area) are reported as infiltrating through the permeable surface thereby recharging

the shallow aquifer (Nyrstar, 2013).

Most of the contamination in Port Pirie is related to Pb, Zn, Cd, and As and to a lesser extent Cu and

Ag. Pb in particular has been identified as one of the most toxic pollutants threatening human health

(McCartor and Becker 2010), and the processes related to the production of Pb and Zn at the

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smelter result in emissions having greater proportions of fine to ultrafine (<0.5µm) particle size

fractions (Csavina et al. 2011). It is these fine to ultra-fine particles that are harder to contain, travel

farther and are absorbed, ingested, and inhaled more readily and consequently have greater

environmental impact potential.

In coastal and marine systems, although airborne particles do contribute to the overall

contamination loading of a system, it is the binding of the contaminants to the sediments that is

likely the highest risk. Metals can be bound to sediments through a variety of mechanisms; in lattice

structures of primary minerals (such as silicates) and secondary minerals like carbonates, sulphates

and oxides; adsorbed onto clay or iron/manganese oxyhydroxides or complexed with organic

matter. Each of the different forms has a different remobilisation potential and hence different

potential bioavailability or toxicity level (Tessier et al. 1979).

Sediments are unusual in that they can act both as a source of metals into the environment and as a

carrier (Zoumis et al. 2001). Some of the controlling factors relating to metal availability are pH and

organic matter. pH is a key controlling factor in metal transfer behaviour in sediments with increased

metal mobility usually being linked to decreasing pH (Zhang et al. 2018). Organic matter

concentrations in sediments plays a large role in potential metal mobility, with formation of metal

soluble complexes with dissolved organic compounds being much more mobile and potentially toxic

than metal ions bound to insoluble organic compounds (Buffle, 1998).

Metals also exhibit differences in the mobility through and within sediment profiles. Metals such as

Zn are more mobile as they are labile or weakly complexed in contrast with other metals (such as Cd)

which are non-labile and strongly complexed (Ferguson 1983, Beesley et al. 2010; Vamerali et al.

2009). Ettler (2016) reviewed over 160 soil contamination studies near non-ferrous smelters and

concluded that Cd and Zn contamination was generally more mobile than Pb, which whilst less

mobile, showed fast downward penetration of the soil profile likely linked to the mineralogical

composition of the Pb particulate matter.

Sediments provide the foundation blocks of many of our food webs within aquatic systems and the

health of sediments have direct bearing on the health of the systems they support. Sediment metal

contamination can cross multiple ecological scales, from the individual, community to ecosystem

levels (Dang et al. 2013; Botter-Carvalho et al. 2014). Previous studies at Port Pirie demonstrated

impaired marine community structures and marine species composition changes directly linked to

metal contamination gradients (Ward 1984, Ward and Hutchings 1986).

Metal contaminated sediments are known to affect organisms living within the sediments

themselves with the toxicity of metals and sediments being directly related to the geochemistry of

the sediments and the biology and behaviour of the benthic organism in terms of physiology and

feeding behaviours (Aleksander-Kwaterczak et al. 2008). Metals associated with precipitates and

suspended particles may accumulate to high concentrations in bed sediments, leading to elevated

metal exposure and potential toxic effects on benthic organisms (Besser et al. 2015). Because

benthic assemblages receive the most comprehensive exposure to the overall environment, they

become one of the most impacted by environmental degradation in aquatic systems (Chapman and

Anderson 2005; Chapman 2007; McPherson et al. 2008; Wu et al. 2014).

In marine systems, the bioavailability of heavy metals is defined as the amount of metals taken up by

organisms, having the potential to cause an effect (Plette et al. 1999). Where the sediment system is

hyper-saturated, the potential for the disassociation of the metals into solution is of particular

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concern and along with constant resuspension at the sediment -water interface, further disturbance

of the sediments (eg through dredging) may also allow the metals to become more readily

bioavailable. Unpublished studies by the EPA (cited by Gaylard et al. 2011) show that the

concentration of bioavailable metals in Port Pirie River was extremely high, with up to 98% of metals

in the water column being bioavailable (dissolved).

The effects once a metal is bioavailable range from lethal toxicity, reduced productivity and

fecundity, and bioaccumulation up the food chain. Ingestion of contaminated sediments is likely to

be a key route of exposure to metals for deposit-feeders such as bivalves (King et al., 2004). Once

organisms take up heavy metals, they must excrete and/or detoxify these metals to avoid potential

toxic effects. Heavy metals that are in excess of metabolic requirements and the organism’s ability to

store internally can be potentially toxic (Rainbow & Luoma, 2011).

Of considerable concern at Port Pirie, is the potential for human health to be affected through

ingestion of contaminated seafood. Ward (1987) showed elevated cadmium, lead and zinc in the

bivalve Pinna bicolor (known locally as a razorfish), which correlated with distance from the smelter,

and concluded that in some locations the levels of zinc in the razorfish exceeded the recommended

Australian National Health & Medical Research Council’s maximum recommended levels for human

consumption of molluscs. The South Australian Research and Development Institute’s Aquatic

Sciences Department, (on behalf of the South Australian Health Commission), also determined that

metal concentrations in razorfish sampled throughout the Port Pirie region exceeded the applicable

food standard (Edyvane & Boxall 1997). In July 1996, in response to concerns over the eating of

contaminated shellfish, the SA Government prohibited the taking of ‘marine benthic Molluscs’ from

the majority of Germein Bay, a ban that remains in place. Further to this, more recent works by the

SA EPA demonstrated that the Pb levels in translocated mussel experiments in the Port Pirie River

were some of the highest recorded in the literature (Gaylard et al. 2011). Whilst mussels as a

‘bottom dwelling Mollusc’ are included under the exclusion zone, little awareness exists in the local

community and they remain a target species for local recreational fishers.

Internationally, a large body of recent work has looked at remediation of metal contaminated

sediments and soils (Birch et al. 2015; Fonti et al. 2016; Gan et al. 2016; Marques 2016; Song et al.

2016 and Zhang et al. 2016) and a separate body of work has looked at recovery from waste

streams of rare, scarce and trace elements which have a higher value when recovered (Bellenfant et

al. 2013; Diallo et al. 2015; Dodson et al. 2015 and Nancharaiah et al. 2016). To our knowledge

little work has examined the potential for metal recovery from contaminated sediments as a way of

offsetting the costs of remediation.

This project undertook broad-scale spatial mapping of metal concentrations in surface sediments

surrounding Port Pirie, supplemented with targeted core sampling to estimate the mass of

contamination (or potential resource) present. Specifically we asked: (i) Are the sediments of Port

Pirie contaminated with metals, (ii) if still contaminated, how far from Port Pirie does the

contamination extend, (iii) what depth does the contamination go, and (iv) is there sufficient

potential value of the metals within the sediments to warrant further examination as a ‘resource’.

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2 Method

2.1 STUDY SITE

The study area (Figure 2) covered an approx. 20 x 20 km2 area bounded by Germein Bay to Ward Spit

with the most western site being approx. in line with Sixth Creek. It included sites adjacent to the

Port Pirie smelter (Figures 3 & 4), on the Port Pirie river, First Creek into which the smelter effluent

discharge pipe runs, and the wider Port Germain marine area. Two background sites were also

included (site 19 at Fisherman Bay and site 20 at Port Davis).

2.2 FIELD WORK

Broadscale field sampling within the Port Pirie area (from Ward Spit down to Fifth Creek and into the

Port Pirie river) was undertaken using a multi-stage field sampling program (Figure 1) to map

contaminants, surface sediment characteristics and environmental condition of the habitats present.

Figure 1 - Project field work and testing details

In conjunction with the EPA, field work was undertaken as detailed within Figure 1. In the initial grab

sample locations both sediment and water quality samples were collected. There were a few sites

where only water quality samples were collected due to sediment grab refusal in seagrass beds.

There were also some sites with sediment samples only as additional samples were collected when

the opportunity arose.

The EPA provided State coastal habitat mapping layers which were amended with recent (Nyrstar

2018) aerial photography. The habitat data was used in conjunction with mapped data points of

previous sampling campaigns undertaken, was used to help plan the initial location of samples. The

results of the grab samples informed the second and third round sampling.

The South Australian Department of Environment and Natural Resources also collected 6 soil

samples within permanent samphire habitat monitoring stations. These additional sites were

analysed for metal content to provide data on the coastal vegetation habitats close to the northern

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smelter stockpiles. These additional sites were not included within calculations of average metal

concentrations due their being terrestrial sites rather than fully submerged marine sites.

2.2.1 Water quality sampling

Surface water samples (Figure 5) were collected in accordance with AS/NZS 5667 Part 9 (Guidance

for sampling of marine waters) were collected at a depth of approx. 15 cm with sterile then 3x rinsed

(in site water) syringe, avoiding any surface scum and debris. The sample was taken upstream and to

the side of the boat, with the syringe gently moved slowly forwards through the water to the

required level.

Once collected, 70ml of the sample was filtered into a labelled clean plastic container. The lid was

closed securely, and each sample placed into a sample bag, storing upright in an ice filled esky. Once

onshore the samples were fixed with 0.1% HCl (v/v) and stored in the fridge at a constant

temperature until transported back to UniSA (on ice).

2.2.2 Sediment sampling

2.2.2.1 Surface grab samples

Initial surface/grab samples were collected 29th Oct-2nd Nov 2018 (Sites 1-65), intertidal cores (No’s

1.0C-15.0C) taken 19-22nd August 2019 and further intertidal cores (No’s 16.0C-22.0C) and targeted

additional grab samples (Sites 66-70) taken 25-27th September 2019. The 62 grab sample surface

sites (using an 3.5L Eckman grab) had the following data collected: observational data, site depth,

water quality parameters (pH, conductivity, salinity and temperature) and sediment samples (where

possible) at each site. Grabs were stratified across habitats - seagrass, mangroves, bare intertidal,

bare subtidal and in the shipping channel/Port Pirie River inlet. At least three grabs were taken from

each habitat, then numbers of samples in each habitat were proportionate to the area of habitats,

albeit with sampling also weighted towards areas which were been identified in historical datasets

with greater metals concentrations from historical sampling.

Sediment samples were taken of the surface sediments and 3 attempts were made at each site.

Where refusal was met each time the attempt for that site was aborted and another site in the

vicinity attempted. 62 sediment samples were attempted, with a small number of sites being in

dense seagrass and therefore not allowing grab sample collection resulting in 57 sites in total.

Samples were extruded into a clean plastic tray and double bagged using clean plastic spatulas. The

samples were then kept on ice within cold boxes until storage within a fridge. Upon return to the

laboratory, each sample was split into 3 (where sufficient sample permitted) for total metal analysis

and total organic carbon (TOC), particle size analysis and, sample volume permitting, a sample

portion for freezer retention. Each sample for total metals and TOC analysis was dried at 80oC until

constant dry weight (DW). The sample was then lightly ground prior to analysis.

Additional grab samples (4) were taken in September 2019 adjacent to Site 5 within the Port Pirie

river. Site 5 was one of the 14 sites randomly selected for size-fraction metal analysis and during this

work additional analytes including silver (Ag) were examined. The results for Site 5 reported very

high Ag (41.84 mg/kg) and as such the site was revisited and 4 additional grab samples taken

(surface sites 66-69).

Another additional grab sample (site 70) was also taken at the boat wreck north of the smelter in the

Port Pirie river as anecdotally this wreck was reported to be an ore barge.

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Figure 2 - Sediment sampling sites (‘C’ indicates deeper core samples were taken). Port Davis (Site 20.0C) and Fisherman’s Bay (Site 19.0C) were included as ‘background’ comparison sites.

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Figure 3 - Sediment sampling sites (‘C’ indicates deeper core samples were taken) excluding background sites. Sites Samph 1-6 are additional samphire habitat sites.

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Figure 4 - Sediment sampling sites within Port Pirie river (‘C’ indicates deeper core samples were taken).

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Figure 5 - Water sampling sites within Germein Bay. An additional sample (5.1) was taken at site 5 in the prop wash of an ore vessel leaving Port.

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2.2.2.2 Deeper core samples

Whilst initially the 22 deeper cores were intended for sampling within a mix of shallow and deeper

waters using SCUBA divers, unfortunately sampling occupational health and safety constraints

(namely an approx. 5m Great White shark which established itself around the First Creek locality

during the sampling periods) resulted in cores only being taken in shallow waters (with deeper

samples intended to be undertaken in future campaigns).

Sallow cores were undertaken at low tide hammering clean 3m PVC tubes into the sediment to

maximum penetration achievable. The depth to the sediment inside and out of the pipe was

measured in order to calculate compaction and then the core was then carefully removed. A cap was

then placed on the bottom and top of the core and taped in place. The cores were transported back

to the mobile laboratory upright where a hole was inserted above the sediment level and the excess

water drained off and the end plugged to reduce sediment oxidation. The compaction equivalence

was then calculated, and the core tube was mechanically cut down the middle exposing the

undisturbed intact sediment core which was then sliced and placed into sterile bags as 10cm

equivalent horizons from the surface.

Complete site location coordinates and site descriptors, including site notes, are contained within

Appendix A.

2.3 STUDY LIMITATIONS

The study site covered approximately 20 x 20 km of the marine and coastal areas adjacent to the

Nyrstar Port Pirie smelter. Although the surface sediments of over 60 sites were examined, this is by

no means comprehensive and any extrapolation of trends between sites can be considered

indicative only. This is especially true as there was a high level of heterogeneity between the sites in

terms of habitat, particle size and type of sediments.

Difficulty was also encountered with grab sampling over seagrass beds. Whilst three attempts at

each site were made as well as moving to patchy seagrass mosaics (as opposed to dense beds), the

difficulties sampling over seagrass resulted in some areas not being sampled. Alternative methods

were tried unsuccessfully including use of a Kajak sediment corer. Future mapping of the deeper

areas and dense seagrass beds will need to consider alternative methods such as the use of a

vibrocore as this is more likely to achieve success in the dense seagrass beds.

That all samples were taken within shallow waters is a significant limitation of this study as it is

unknown if the same patterns of metal contamination and distribution will apply in the deeper

channel areas.

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2.4 LABORATORY ANALYSES

2.4.1 Particle size analysis

Samples were analysed for soil grain-size using a Malvern Mastersizer 2000 laser-diffraction particle

analyser following the manufacturers guidelines and ISO13320 (1999) to provide an accurate

representation of the particle size distribution of the site. Results were then grouped in to 4 size

classifications (<63µm, >63µm and <250µm, >250µm and <2mm and >2mm).

2.4.2 Carbon/Nitrogen/Sulphur (CNS) estimation

Total Organic Carbon was calculated as well as nitrogen (N) and sulphur concentrations (S) with use

of a LECO Trumac carbon/nitrogen/sulphur (CNS) determinator following UniSA (2017a and 2017b)

protocols. The Total carbon (TC) and total organic carbon (TOC) and inorganic carbon (IC) contents

of a sample are determined in two separate runs. The first run total carbon was determined as per

the routine dry combustion method. A known quantity (0.2g) of dried sediment was then placed in a

crucible with sulphurous acid dropwise until covered, placed into a furnace, and left to dry. The

sample was then removed and cooled. This process was repeated until no further bubble reaction

occurred. The second run determined TOC after IC has been removed by Acidification. The acid

addition and drying step was then undertaken a final time, and the sample was then analysed. The

inorganic carbon is then calculated as the difference between the TC and TOC values. %IC =%TC- %

2.4.3 Total metal concentration

2.4.3.1 Water quality samples

Water samples were syringed and filtered through 0.45 µm disposable filters into 10ml ICP sampler

tubes for metal analysis. Concentration of elements (Pb, Zn, Cu, Cd, Cr, Co, As, Ni, Mn, Fe, Ti, S and

Si) were measured using Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES) at

the University of South Australia Future Industries Institute.

2.4.3.2 Sediment samples

Dried and homogenized sediment (0.5g) was weighed into Teflon microwave digestion vessels and

pre-digested overnight with a reverse aqua regia solution (3.75ml HNO3: 1.25ml HCl), which was

necessary due to the high quantities of calcium carbonates in many of the samples. The sample was

then microwave digested at 175oC (as per EPA method 3052 (USEPA 1996). Digested samples were

cooled for at least 30 min in the fume hood, and the digest transferred to a tubes and diluted up to

50 mL with Milli-Q water.

Diluted samples were allowed to settle for at least an hour and then syringed and filtered through

0.45 µm disposable filters into 10ml ICP sampler tubes for metal analysis. Concentration of elements

(Pb, Zn, Cu, Cd, Cr, Co, As, Ni, Mn, Fe, Ti, S and Si) were measured using the ICP-OES.

To control for possible ICP-OES interferences due to the presence of the acid solution, a sample and

a blank were spiked with 1ml 100ppm QC27 and run in parallel to the samples along with a blank

aqua regia sample and a standard reference material (NIST 2702 Inorganics in Marine Sediment).

Good analytical precision was obtained, with an average relative standard deviation (RSD) of 2% for

duplicate analyses for each element. The recovery of the elements was satisfactory (average 99%).

Certified and measured values of the standard reference material NIST 2702, percentage of recovery

and limits of quantification (LOQs) were calculated for each chemical element.

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For those fourteen samples that were chosen for size-fraction metal analysis, the individual size

fractions were microwave digested and analysed by ICP-OES (as detailed above). For those samples

and the core samples, silver (Ag) was added into the analyses metal suite. In the initial surface

samples Ag was not included as it had not been recorded previously as being present in significant

concentrations in the marine sediments.

2.4.4 Spatial analysis

Metal concentration results are presented in Table X and spatially mapped using the ArcMAP

(version 10.6) mapping software to present spatial point data relating to Pb, Zn, Cd, As, Cu and Ag

concentrations. PDF’s are provided which present ‘clickable’ layers illustrating the concentrations at

selected depths (0-10cm, 20-30cm, 50-60cm, 80-90cm, 110-120cm) with the full depth data for each

site and metal provided within associated project Microsoft Excel spreadsheets.

2.4.5 Resource estimation

Broad initial calculations were undertaken for key areas where metal concentrations were

significant. The results use current (July 2020) ore values with two scenarios for sediment grain size

to assess potential value. As the site was so variable in terms of sediment types, some assumptions

were required as to sediment type, portion / fraction that the metals are held within and the depth

of the contamination. The calculations necessarily approximate concentrations across a site with

non-optimal sampling distribution to give some prediction of potential resource recoverability.

13

3 Results

3.1 WATER QUALITY

As detailed within Section 2.2.1, water quality observations and samples were undertaken at 61 sites

between the 29th October- 2nd November 2018. Unfortunately, on downloading it was noted that

the data logger failed to take readings at several sites (10) so observational data was collected for 51

sites. Site 5.1 was an opportunistic sample taken within the prop wash of a large ore shipment as it

passed.

pH averaged 8.2 (range of 8 to 8.3). Water temperature ranged between 17.9 and 23.8oc with a

mean of 20.3oc, with salinity between 41.1 and 45.8 ppm (average of 43 ppm) which concurs with

others observations for the Upper Spencer Gulf of 42 – 47ppm (Australian Bureau of Meteorology,

2016) depending on season (Table 1).

Site Temp oc Salinity ppm pH Chl Site Temp oc Salinity ppm pH Chl

1 23.5 44.8 8.2 2.4 35 18.8 41.7 8.2 22.1

4 23.8 45.0 8.2 1.4 36 18.5 41.6 8.2 0.6

5 23.5 44.6 8.2 2.1 37 18.9 41.9 8.2 0.8

6 19.3 42.9 8.2 0.4 38 21.3 42.1 8.3 0.9

7 19.3 42.9 8.3 0.7 41 19.4 42.8 8.2 1.0

8 19.2 43.2 8.2 -0.3 47 20.0 43.8 8.2 17.2

9 19.4 42.8 8.2 0.9 48 18.6 44.6 8.2 1.8

11 20.2 42.9 8.2 0.6 49 19.0 43.8 8.3 1.4

15 20.0 42.2 8.2 0.5 50 19.1 43.9 8.3 1.6

18 17.9 45.3 8.2 20.0 X1 19.0 44.6 8.3 1.4

19 19.2 44.3 8.3 1.1 X2 19.5 42.3 8.2 0.8

20 20.0 44.3 8.2 1.9 X3 18.7 41.6 8.2 0.6

21 23.0 44.2 8.3 1.8 X4 19.3 41.8 8.2 5.5

22 18.7 41.5 8.2 0.6 X5.1 19.0 42.0 8.2 3.0

23 18.8 41.6 8.2 2.0 X6 21.4 43.7 8.3 1.5

24 22.1 42.4 8.2 -0.3 X7 20.1 41.7 8.2 0.7

25 19.4 42.2 8.3 1.1 X8 21.4 42.4 8.2 0.5

26 19.1 41.1 8.2 0.4 X9 20.4 42.0 8.2 0.9

27 18.8 41.5 8.2 0.7 X10 22.8 44.4 8.2 2.2

28 20.3 42.8 8.2 0.9 X11 22.6 44.8 8.2 1.9

29 21.2 42.5 8.3 1.6 X12 22.8 45.8 8.0 1.3

30 19.0 41.6 8.2 0.6 X13 21.7 42.6 8.1 1.9

31 19.4 41.7 8.3 0.9 X14 23.1 44.9 8.1 2.3

32 19.3 41.8 8.2 0.5 X15 23.4 44.6 8.2 2.7

33 19.1 42.0 8.2 1.0 X16 22.7 44.0 8.2 2.5

34 20.4 42.4 8.3 0.8

Table 1 - Temperature, salinity, pH and chlorophyll levels at study sites

Results are reported against the ANZECC & ARMCANZ (2000) default guideline values 95% and 80%

level of species protection. The DGV’s for toxicants were derived using species sensitivity distribution

(SSD) approaches and provide guideline values for 99, 95, 90 & 80% species protection depending on

the current (or desired) condition of the system. The decision was made to use the 80th and 95%

14

level of protection as the Port Pirie marine system is considered to be a moderately to highly

disturbed system (Appendix Table B).

PDF No. 1 (PDF 1_Water_Metals.PDF) illustrates the metal concentrations for As, Cd, Cu, Pb and Zn

across the study area with Appendix B containing the tabulated data.

No sites reported cadmium concentrations over the 80% or 95% level of species protection. Whilst

Cd was not over the 95% level of 5.5 µg/L, it routinely occurred in samples and was over the 99%

level of species protection value of 0.7 µg/L specified within the ANZECC & ARMCANZ guidelines.

No reliable marine trigger exists for arsenic, but three sites exceeded the working value for arsenic

of 4.5 µg/L for As (V). These three sites (sites 5, 20 and X12) are all within the Port Pirie river and

reported high concentrations for the other metals tested. Site X12 was located within a mangrove

tributary on the eastern side of the Port Pirie river.

More information, including good Australasian species data, on the toxicity of Zinc has resulted in

updated (June 2020) default guideline values (GVs) of 5.2 µg/L and 16 µg/L 95 for the 80% species

protection, respectively. Elevated concentrations can reduce growth and reproduction and increase

mortality (Hogstrand 2012), and in invertebrates, zinc appears to inhibit oxygen consumption rates

and disrupt ammonia excretion (Cheung & Cheung 1995, Wu & Chen 2004), with elevated

concentrations can lead to reduced growth rates and mortality (Li et al. 2016). Adsorption of zinc to

suspended particles, and the consequent sedimentation of these particles, is a major route of

removal for zinc from the water column (Stumm & Morgan 1996). However, at Port Pirie where

sediment Zn concentrations are significantly elevated enough to be considered ‘hyper-saturated’

with few binding sites available, Zn in the water column is likely to be high. This is evidenced in the

results where 100% of the sites sampled reported Zn levels over the 95% species protection level of

5.2 µg/L with over 57% of these sites over the Zn 80% species protection value (16µg/L). The Zn

levels at Port Pirie (max of 87.9 µg/L) are less that those shown to cause acute toxicity in marine

species recorded as ranging from 170 μg/L to up to the solubility limit based on 24-h to 96-h LC50

and EC50 values (USEPA 1987, 1996). Chronic toxicity has been reported at much lower levels, with

some of the most sensitive species being diatoms and green algae. For example, Maycock et al.

(2012) calculated EC10s for two diatom species of 1.4–70 μg/L for Skeletonema costatum and 2–47

μg/L for Asterionella japonica. Cnidarians have also been also reported to be highly sensitive to zinc

exposure, with a 28-d EC10 of 9 μg/L for reproduction and development of the anemone Aiptasia

pulchella (Howe et al. 2014).

Lead is generally present in very low concentrations in marine waters as it is adsorbed strongly by

suspended clay, humic substances and other suspended matter. Approx. a third of sites reported Pb

concentrations over the 95% species protection level of 4.4 µg/L., with 12% of the sites over the 80%

species protection value of 12 µg/L. As with Zn, the hyper-saturation of the sediments by Pb at Port

Pirie is likely contributing to the high levels within the water column. Acute toxicity effects for 13

marine animal species (as examined by the ANZECC/ARMCANZ water quality guidelines, 2000)

ranged from 315 μg/L (mummichog) to 27 000 μg/L (soft-shell clam). The maximum value recorded

in this study was 43.1 µg/L which although less than values observed for acute toxicity, is higher than

concentrations recorded as causing chronic toxicity effects on mysids (observed at 37 μg/L), and

macroalgae which were affected at 20 μg/L (USEPA 1985).

Copper, which is of significant concern in marine waters due to its high toxicity, was reported at

nearly half of the sites over the 95% species protection value of 1.3 µg/L with 5% of sites exceeded

15

the 80% species protection level (8 µg/L). Site X8 (offshore from First Creek) had a Cu value of over 6

times the 80% trigger value, and two other sites within the Port Pirie river area also had values

greater than the 80% trigger value. Acute toxicity of Cu to marine crustaceans for concentrations as

low as 10µg/L have previously been recorded as causing sublethal effects, and acute LC50 values for

prawns, crabs and amphipods have been recorded in the range of 100-1000 µg/L, with chronic

values from 10-300 µg/L (Arnott & Ahsanullah 1979, Ahnsanullah & Florence 1984). Toxic effects are

not restricted to fauna either with effects on marine algae also observed for Cu concentrations as

low as 5 µg/L and 100 µg/L (USEPA 1985).

High Pb, Zn and Cu concentrations were often reported in conjunction with each other, with 59% of

sites having two metals over the 95% species protection value (and 24% of sites having 3 metals over

the 95% SPL). Again sites 5, 20 and X12 had significantly elevated levels of all metals. Whilst there is

conjecture in the literature about whether combination effects of metals, some studies have

reported that toxicity of Pb, Zn and Cd in combination is additive depending on species (Cooper et al,

2009).

When the distribution of the metals is examined, the Port Pirie river, river mouth and mid Germein

Bay reported the highest metal contamination. Those sites to the north and west of Port Pirie (for

example sites towards Ward Spit or the far west) showed much lower levels of metal contamination

in the surface waters. This agrees with previous works which also reported that sites closer to the

smelter had higher metal contamination which decreased with distance from the smelter (Ward et

al. 1984).

This represents a snapshot of water quality as tides, currents and water movement water movement

from wind, tides and currents can influence water metal concentrations (as can rain events and

effluent discharge flows after rain events). Long-term studies encompassing multiple tidal ranges

and season will be required to give a clearer prediction of metal concentration patterns at Port Pirie.

The guideline trigger value protection levels (95% and 80% as used in this study) signifies the

percentage of species expected to be protected. For ecosystems that are classified as highly

disturbed (such as the Port Pirie river), the guidelines suggest that the 95% protection trigger values

still be applied, which is why both were presented in Appendix Table B. It is of significant concern

that Zn, Pb and Cu all had a significant number of sites that exceeded the 80% trigger value.

16

3.2 SEDIMENT QUALITY

All sediment metal concentrations were compared to the ANZECC & ARMCANZ (2000) sediment

default guideline values, and where applicable, the revised sediment quality guidelines (Simpson et

al. 2013). Sediment values, unlike the water quality values, were not derived from species sensitivity

distributions (SSDs) of chronic toxicity data as only limited sediment toxicity test data were available.

Instead, ANZECC & ARMCANZ (2000) derived DGVs using a ranking of both field ecological and

laboratory ecotoxicity-effects data from North America with the DGV representing the 10th

percentile value of the data distribution and using the median value as an additional upper guideline

value (GV-high) (ANZECC & ARMCANZ 2000).

The sediment DGVs indicate the concentrations below which there is a low risk of unacceptable

effects occurring. The ‘upper’ guideline values (GV-high) provide an indication of concentrations at

which toxicity-related adverse effects are likely to be observed, and is an indicator of potential high-

level toxicity problems, not as a guideline value to ensure protection of ecosystems. The upper

guidelines (SQG‐High) are mostly based on the effects‐range median (ERM) values (for metals) (Long

et al., 1995) and the total concentration (TC, mg/kg dry weight) of the individual chemical

contaminant in the sediment is compared to its SQGV-low and SGQV‐high values. Where total

contaminant (TC) concentration is less than the SQGV-low effects are likely to be negligible; where

TC is great than the SQGV-low and less than the SQGV-high then effects are possible and where TC is

greater than the SQGV-high then biological effects are expected on the organisms inhabiting that

sediment (Simpson et al, 2013).

3.2.1 Historic metal concentrations

Previous sediment data from the literature was compiled for comparison to results reported within

this study. A total of 60 papers (from 1970 to 2019) were identified examining the impacts of the

smelter upon the marine and coastal environment of Port Pirie and the wider Port Germein locality.

However, the field work of over 50% of the papers was between 1973-1983 (over 50%). Only 4

papers contained field data in the past 10yrs with most relating to small dredge works within the

Port Pirie river.

Those papers with relevant locational data were combined into a single database, with the historic

metal concentrations mapped (PDF 2_Historic data.pdf). The historic data places the smelter at the

centre of the greatest Pb and Zn concentrations, with distance being the greatest driver in reduced

metal concentrations. The Port Pirie river is the area with the highest metal concentrations, likely

due to its proximity to the smelter stockpiles, the stack aerial emissions and the loading / unloading

from the wharfs.

Early studies (Thomas 1972, 1978) reported extremely high Pb and Zn concentrations (37,000 mg/kg

of Zn and 5-22,000 mg/kg Pb) usually at, or very close to the smelter operations, with the CSIRO led

papers (Ward 1981) reporting Pb and Zinc at levels in the 1000-4000 mg/kg range.

Elevated levels were also reported in the area north of the river mouth near Weerona Island. Three

historic dredge disposal areas (Figure 6) exist which were utilised through the 1980’s and 1990’s for

dredged sediment from the river boat ramps, wharfs and berth pockets/ turning circles for the Port.

The higher levels in the mid-bay adjacent to the shipping channel may have been linked to these

disposal areas.

17

The areas north of First Creek and the river mouth also showed higher concentrations of Pb and Zn.

Areas towards Ward Spit and to the west of second creek appear to have much lower levels of

metals reported.

A number of studies under taken by CSIRO (Ward & Young 1981, Ward & Young 1982, Ward et al

1986, and Ward 1987) examined the impacts of the metals contamination at Port Pirie upon the

ecosystem including examining sediment, seagrasses, epifauna, crustaceans and fish. A significant

relationship was found between the geographical patterns of Cd, Pb and Z in the species measured

with distance from the smelter. Nearly all species also showed patterns of bioaccumulation although

no biomagnification was observed. Community structure was also significantly altered with 20

species of fish and crustaceans found to be eliminated or reduced in numbers in those sites with

significant metal contamination (Ward & Young 1982). Seagrasses at Port Pirie also highlighted as

being major accumulators of Zn (along with Pb and Cd) and attributed as a major source of metal

transfer to fauna through detrital food webs (Ward et al 1986).

Figure 6 -Historic dredge disposal areas (approximate locations from Wagstaff 1983) with current

sediment site locations.

18

3.2.2 Particle size analysis

Two different methods were utilised to assess particle size in the sediment surface samples. The

Mastersizer was used to assess the PSA of all the surface samples. Alongside this, wet sieving was

used to separate surface samples from 14 sites of the sites in order that the metal concentration

could be calculated within each of the 4 size fractions.

The results from the size fraction metal content work are contained within Section 3.3.4. Full particle

size proportions are given in Table 5.

The results were generally as expected with mangrove inlets and the Port Pirie river having fine

sediment driven environments, and mid-bay areas showing the highest variability to each other

(likely driven by presence or absence of seagrass). This can be contrasted with the areas in the

eastern shallows and north/eastern shallows (towards Ward spit) which were driven by larger

sand/shell gravel sediments.

The two samples in the reclaimed fill area (opposite the smelter over the Bridge to Nowhere) were

very different in composition to each other with site 64 comprising largely of >200 microns particles,

and site 65 which was comprised largely of smaller fine sediments (<36 microns).

The results from the PSA by Mastersizer and wet sieving broadly concurred with one another

although it is apparent that, whilst all care was taken, wet sieving lost a portion of the finest

sediments during sample preparation.

3.2.3 Surface metal concentrations

Pearson's correlation coefficient (r) is a measure of the strength of the association between the two

variables and was used to examine the relationship of the metal concentrations within the surface

sediments to one another. Data were tested for normality using a Kolmogorov-Smirnov test and

were log-transformed as the data was not normally distributed.

Multi-Dimensional Scaling (MDS) was then used to map the dissimilarity of the metals to one

another. The purpose of multidimensional scaling (MDS) is to provide a visual representation of the

pattern of proximities (i.e., dissimilarities or distances) among a set of variables. When the points are

plotted on a map, those metals that are perceived to be very similar to each other are placed near

each other on the figure, and those metals perceived to be very dissimilar from each other are

placed far away from each other.

As demonstrated both in Table 4 and Figure 8, Pb, Zn, Cd, Cu and As are strongly similar to each

other, with the Pearson’s correlation coefficients over 0.82 indicating high similarity. Pb and Zn are

very highly correlated with a Pearson correlation coefficient of 0.957. Al and Fe are also highly

correlated with each other (PCC of 0.967) and Al, Fe and Ni also appear to be more similar to each

other than to Pb, Zn, Cd, Cu and As. Mn doesn’t seem to be strongly associated with any of the other

metals and Co and Cr are similar to each other but dissimilar to any other metals.

Table 5 present the surface metal concentrations recorded from survey grab sites, additional grab

sites and the top (surface) horizon of the core sites. Results are discussed for Pb, Zn, As, Cd, Cu and

Ag as these metals that have levels of particular concern though results for the other metals are

shown in Table 1.

19

Al mg/kg

As mg/kg

Cd mg/kg

Co mg/kg

Cr mg/kg

Cu mg/kg

Fe mg/kg

Mn mg/kg

Ni mg/kg

Pb mg/kg

Zn mg/kg

Al mg/kg 1 0.656 0.602 0.639 0.592 0.640 0.976 0.670 0.869 0.663 0.684 As

mg/kg 0.656 1 0.744 0.419 0.211 0.848 0.733 0.729 0.782 0.822 0.846 Cd

mg/kg 0.602 0.744 1 0.480 0.338 0.790 0.655 0.725 0.562 0.855 0.925 Co

mg/kg 0.639 0.419 0.480 1 0.877 0.480 0.693 0.671 0.506 0.488 0.503 Cr

mg/kg 0.592 0.211 0.338 0.877 1 0.347 0.602 0.508 0.391 0.356 0.353 Cu

mg/kg 0.640 0.848 0.790 0.480 0.347 1 0.720 0.769 0.751 0.859 0.858 Fe

mg/kg 0.976 0.733 0.655 0.693 0.602 0.720 1 0.758 0.879 0.730 0.744 Mn

mg/kg 0.670 0.729 0.725 0.671 0.508 0.769 0.758 1 0.633 0.770 0.802 Ni

mg/kg 0.869 0.782 0.562 0.506 0.391 0.751 0.879 0.633 1 0.648 0.660 Pb

mg/kg 0.663 0.822 0.855 0.488 0.356 0.859 0.730 0.770 0.648 1 0.957 Zn

mg/kg 0.684 0.846 0.925 0.503 0.353 0.858 0.744 0.802 0.660 0.957 1

Table 2 - Proximity matrix (Pearson correlation coefficient) for individual metals in Port Pirie surface sediments.

Figure 7 - Map of dissimilarity for a 2-dimensional representation in space for individual metal concentrations in Port Pirie surface sediments.

The accompanying PDF’s (PDF’s 3-14) contain the mapped concentrations for the surface (0-10cm)

metal concentration results for Pb, Zn, Cd, Cu, As and Ag along with selected depth horizons for each

core site (depth horizons 20-30cm, 50-60cm, 80-90cm and 110-120cm). For each PDF / metal the

results are classed in to 5 concentration groupings: < background, greater than the ANZECC &

ARMCANZ (2000) GV-low, > ANZECC & ARMCANZ (2000) GV-high and then other nominated values

of increasing concentration depending on the metal.

Al mg/kg

As mg/kg

Cd mg/kg

Co mg/kg

Cr mg/kg

Cu mg/kg

Fe mg/kg

Mn mg/kg

Ni mg/kg

Pb mg/kg

Zn mg/kg

-0.3

-0.2

-0.1

0

0.1

0.2

0.3

-0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4Dim

2

Dim1

Configuration (Kruskal's stress (1) = 0.078)

20

3.2.3.1 Lead

55 of the 84 surface sites examined (66%) of surface samples had Pb concentrations the GV-low

value (50 mg/kg) and 39% of the sites over the GV-high value (220 mg/kg). All sites within the Port

Pirie river/mouth and First Creek vicinity were above the GV-low with sites closest to the smelter in

the Port Pirie river being the most impacted (sites 16C-18C had Pb values between 4000-9200 mg/kg

– between 20 and 40 times the GV-high value).

3.2.3.2 Zinc

Zinc had a similar distribution as Pb and Cd with 56% of total samples with concentrations over the

GV-low value of 200mg/kg and 44% of the total samples over the GV-high value of 410 mg/kg. As

with Pb, nearly all sites within the Port Pirie river/mouth and First Creek vicinity were above the GV-

low with sites closest to the smelter in the Port Pirie river being the most impacted with site 16C

(slightly north of the smelter site) reporting a Zn value of over 21,000mg/kg (over 50 times the GV-

high value).

Whilst Zn is not usually considered as being as toxic as Cu and Pb, studies have demonstrated

impacts upon carbon fixation in phytoplankton (Davies and Sleep 1979), inhibition of diatom growth

(Stauber & Florence 1990), impacted larval settlement and metamorphosis (Bryan et al 1987, Hunt &

Anderson 1989) and impacts on species fertility (Ojaveer et al 1980).

3.2.3.3 Cadmium

The results for elevated cadmium concentrations appear to be linked to both those of Pb and Zn

with most samples reporting elevated concentrations for all metals. 65% of samples were above the

GV-low of 1.5 mg/kg and 28% of the total samples were above the GV-high value of 10mg/kg. Of the

37 sites situated within the Port Pirie river/mouth or First Creek locality, 35 reported cadmium above

the GV-low.

Of note is that the ANZECC & ARMCANZ guidelines for cadmium recommend use of the 99%

protection level of 0.7 mg/kg for slightly to moderately disturbed ecosystems. If this value were

adopted (rather than the 95% protection value as adopted for the other metals) then 75% of the

sites would be over the GV-low.

Elevated sediment Cd levels have been shown to impact on reproduction rates in marine species

(Paffenhofer & Knowles 1978), inhibit growth in flatfish (Westernhagen et al 1980) and

phytoplankton growth inhibition. In the common limpet Patella vulgata, elevated Cd levels inhibited

glucose uptake resulting in reduced growth (Shore et al. 1975). High levels of Zn however appear to

suppress Cd uptake through competition for metal-binding sites (Bryan et al 1985)

3.2.3.4 Copper

12 sites (14%) reported Cu concentrations above the GV-low of 65mg/kg. Site 18C reported a Cu

concentration of 490.98 mg/kg nearly twice the GV-high value of 270 mg/kg. All the sites reporting

elevated Cu were within the Port Pirie river/mouth or First Creek locality. Where Cu was present,

there were also high concentrations of Pb, Zn, Cd, As and Ag. During the derivation of the revised

sediment guidelines (Simpson et al., 2013), inclusion of a range of acute and chronic effects data for

copper (based on silty sediments) for a range of trophic level organisms were included. From this it

was concluded that adequate protection for all benthic organisms could be expected to be achieved

for an OC‐normalised copper concentration of the <63 μm sediment fraction particulate copper

21

concentration of 3.5 mg Cu/g OC and when dissolved copper in sediment pore waters or overlying

waters is below 3 μg Cu/L. Given that size fraction studies (Section 3.2.4) indicates Cu concentrations

(within the <63µm size fraction) range from 6.91 – 143.91 mg/kg (average of 30.95mg/kg), with this

equating to a normalised concentration of 3095 mg Cu/g OC it is likely that the benthic organisms,

particularly in Zone 1, will be significantly impacted by the Cu concentrations.

3.2.3.5 Arsenic

Arsenic had a slightly different distribution than the other metals with 22 sites (26%) reporting

values over the SQL-low value (20mg/kg) and four sites (4.8%) over the GV-high (70mg/kg). All sites

bar one with elevated arsenic levels were in the Port Pirie river/mouth or First Creek vicinity. The

other site (Site 39) was located mid Germein Bay.

3.2.3.6 Silver

Whilst silver was not initially included in the surface sample analysis, subsequent size fraction

analysis on 14 of the samples highlighted that Site 5 within the Port Pirie river had silver levels ten

times higher than the silver ANZECC/ARMCANZ 2000 SWGV-high value and 40 times higher than the

ANZECC/ARMCANZ 2000 SWGV-low value. The additional grab samples taken around Site 5 (sites 66-

69) reported Ag values between 4 and 10.6 mg/kg (and over the SQGL-high value of 4mg/kg).

High concentrations of silver are important in terms of asset recovery potential and all subsequent

analysis included silver (all cores horizons and the additional targeted grab samples around Site 5).

Of the 41 surface samples examined for silver, 39% of the samples reported values over the SQGL-

low value and 25% over the SQGL-high value of 4mg/kg. 13 of the 16 sites reporting exceedances

were in the Port Pirie river/mouth or First Creek vicinity.

22

3.2.3.7 Distribution of metals across Germein Bay

On examination, the site metal concentrations appear to follow a concentration gradient with

distance from the smelter across the Germein Bay / Port Pirie area (PDF’s 3-14). The sites were

grouped into ‘impact zones’ where Zone 1 (red) = high metal concentrations where 86% of the sites

reported metal conc. over the GV-high for 2 or more metals (and 24% had 4 or more metals over the

GV-high); Zone 2 (amber) = intermediate metal concentrations where 75% of sites reported a metal

concentration value over a GV-low, and Zone 3 (green) = low metal concentrations where 86% of

sites had no exceedances of guideline values.

Figure 8 - Zones as grouped by metal concentrations where red = high metal contamination (most sites over GV-high for 2 or more metals), amber = intermediate metal contamination (most sites with one or more metal over GV-low) and green = low contamination levels (few sites with GV exceedances).

Zone 1

Zone 1 (coloured red) is the most impacted / highest metal concentration area and stretches from its

western border between Second and Third Creek up to a line running out from Weerona Island and

23

encompasses the Port Pirie river and mouth, First Creek and those areas directly influenced by their

flows. Most Zone 1 sites exceeded both the ANZECC & ARMCANZ (2000) sediment GV-low and high

for Pb, Zn, Cd and As (as well as Cu when Pb/Zn were extremely high).

All sites within the Port Pirie river reported extremely high levels of Pb, Zn, Cd and As, with most also

reporting Cu values when the Pb and Zn levels were particularly high (>2000 mg/kg). The sites at

First Creek (sites 6.0-8.0C) and directly influenced by its discharges (sites 42-45) had nearly all

surface occurrences of Zn, Pb and Cd levels over the GV-high value. A difference was observed

between the First Creek influenced sites and the Port Pirie river sites, with Cu only having one site

(site 6.0C) reporting a GV exceedance.

That so many of the sites within Zone 1 are above the GV-high value is of significant environmental

concern, as the GV-high provides an indication of concentrations at which toxicity-related adverse

effects are likely to be observed, and is an indicator of potential high-level toxicity problems with

biological effects expected on the organisms inhabiting that sediment (Simpson et al., 2013).

Zone 2

This area contains those mid-bay sites with intermediate metal concentrations with its western

border extending from Zone 1’s and stretches from Weerona Island at Zone 1’s northern border up

to Port Germein in the north. Many of the sites in the mid-bay area west and north of Weerona

Island moving towards Port Germein exceeded the GL-low values for Pb, Zn with many sites also

reporting exceedances for Cd.

Metal concentrations within Zone 2 are of concern as total concentrations greater than the SQGV-

low but less than the SQGV-high have an increased possibility of biological effects upon the

organisms inhabiting that sediment (Simpson et al., 2013).

Zone 3

The eastern edge runs from between Second and Third Creek up to Ward Spit and all sites to the

west. No sites within Zone 3 exceeded the ANZECC & ARMCANZ (2000) sediment guidelines for any

metals.

When the surface sediment metal concentration are grouped and sorted according to Zones 1-3

(Table 6), all the sites with concentrations above the ANZECC & ARMCANZ (2000) sediment GV-high

are contained within Zone 1, most sites with intermediate contamination (above the GV-low but

below the GV-high) are within Zone 2 and few sites in Zone 3 report exceedances above the GV-low.

Whilst many of these samples demonstrated levels above what would be considered background,

the concentrations in waters and sediment are unlikely to be toxic to marine organisms (Simpson et

al. 2013).

24

3.2.4 Metal concentrations in deeper layers (shallow waters only)

As detailed previously, 22 sediment cores were taken at sites within shallow waters of the Port Pirie

marine system. Two additional background cores were also taken at Fisherman’s Bay and Port Davis

to the south of Port Pirie. Within the Port Pirie locality, the most northern core was from the beach

at Port Germein, the most easterly was from the beach at Weerona Island. Site 9.0C at Third Creek

was the most western site. All cores were restricted by necessity to shallow waters. Unfortunately,

health and safety concerns for the survey team resulted in diving being removed from the study

methodology. Further work will be needed to examine deeper sediments across Germein Bay,

particularly in the shipping channel and previous dredge disposal areas.

The accompanying PDF’s (No.’s 3-14) have selected depth horizons metal results from the cores as

clickable layers (0-10cm, 20-30cm, 50-60cm, 80-90cm and 110-120cm) for Pb, Zn, Cd, Cu, As and Ag.

Full core depth data can be found in the provided spreadsheets in which the data is sorted into both

depth (Depth split data200620.xlsx) and site (Data by location200620.xlsx).

The cores vary in depth depending on how far the core could be hammered into the sediment until

refusal (refusal was usually due hitting the impenetrable stiff clay layer). Depths ranged between

0.5m (site 17) and 1.7m (site 13) and 16 of the 22 cores achieved at least 1m in depth. It should be

noted that a lack of data on the PDF map for a core does not indicate no elevated metal

concentration at that site, rather it simply means that no sediment sample was collected at that

depth. Where sediment cores did have a sample at that depth the concentration is presented.

As discussed within the surface sediment metal section (Section 3.3.2), a clear pattern is apparent

Zone 1 containing the Port Pirie river, river mouth and First Creek cores having the highest metal

contamination levels with many sites reporting surface Pb, Zn, Cd, Cu and As over the ANZECC &

ARMCANZ (2000) sediment guidelines in the surface level (0-10cm). This pattern then continued

through the core for varying depths. Generally, the Port Pirie river cores and First Creek cores had

contamination penetrating further down the sediment core than the cores with elevated metal

levels from elsewhere.

The bulk of the metal concentrations in at sites reporting values above ANZECC & ARMCANZ (2000)

sediment GV’s were contained in the top 60 cm. For those sites that had intermediate Pb and Zn

contamination (ie values that lie between the GV-low and high values and largely within Zone 2), the

contamination was largely contained in the top 20cm. Even at the Zone 1 sites when the surface

contamination was 50 x the GV-high (as was the case for Pb at Site 18.0C), the contamination was

only recorded in the top 70cm.

First Creek had a slightly different pattern of contamination than the other Zone 1 sediments with

the highest level of contamination not found in the surface layer (Pb and Zn were highest at 10-30cm

deep for Site 6.0C and from 30-90cm for Zn at Site 7.0C). It should be noted that First Creek has

receives all effluent from the smelter site, and the smelter has a history of accidental spills and

releases (including acid spills which can result in metals dissociating from the sediments to which

they are bound). Sediments within First Creek cannot be considered as undisturbed or operating in a

marine normal system and historic releases may have resulted in the core differences.

For those sites with metals over the ANZECC & ARMCANZ (2000) sediment guidelines, the

concentration of the metals decreased through the core at most sites. There were a few exceptions

to this however with the First Creek sites 6.0C & 7.0C reporting higher concentrations in its mid-

25

layers between 30-90cm of Pb, Zn, Cd and Ag. Site 6.0C also had As levels above the GV-low through

the core to 60-70cm.

Site 18.0C was unique in that it had variable patterns in the elevated concentrations with depth (its

highest Pb, Zn and Cd were at 40-50cm) and very high arsenic levels down to 50-60cm (but

particularly in the 20-40cm horizon). Site 18 is within a recorded fill area (previous dredge spoil)

located over the Bridge to Nowhere and as such shows a very unusual sediment profile.

Other than one erroneous Cd result at 60-70cm depth at Port Davis (site 20), the cores taken at sites

further away from the smelter (sites 19-22) reported no level of metals over ANZECC & ARMCANZ

(2000) sediment guidelines at any depth.

3.2.5 Metal concentrations in size fractions (limited study)

A random sub-sample of 14 of the surface grab samples were wet sieved into 4 size fractions (<

63µm, >63 - <250µm, >250µm - <2mm and >2mm). Each fraction was then analysed for total metal

content. The grab sample sites were chosen for the size fraction work as there was sufficient sample

remaining after the initial PSA, CNS and total metals work.

Figure 9 - Proportion of each sediment size fraction for site divided into sub-fractions for metal analysis

Site 5

Site 13

Site 14

Site 26

Site 28

Site 39

Site 42

Site 43

Site 46

Site 48

Site 53

Site 59

Site 61

Site 64

<63µm >63µm - <250µm >250µm - <2mm >2mm

26

Although difficult to compare the PSA by Mastersizer and the PSA by wet sieving results as the

Mastersizer method required removal of the >2mm fraction, a comparison between the sites shows

a good degree of similarity in the patterns of size distribution. The wet sieving method did result in

an underestimation of the fines (<63µm) proportion of the sample.

There was a high degree of variability between the sites and their size fractions. As was

demonstrated earlier in the PSA section, even sites within the same area show a high degree of

variability and it is likely that the sediment size distribution has more to do with the habitat type

than the location. Areas within the Port Pirie river (site 5) showed higher proportions of fine

sediments, as did the mangrove-lined creeks off the river (sites 59 & 61). Throughout the mid-bay

area, the sites with higher fines are more likely to be in current or historical seagrass beds. The areas

to the west or towards Ward spit had more larger size fractions. Once again (as with the PSA

Mastersizer results), the sample within the area of fill opposite the smelter on the bank of the river

had different size distribution than other sites.

The metal concentration results (Table 7) confirmed that the metals of concern are Zn, Pb, Cd, Cu

and As in that order by concentration. Two sites had no metals exceed the ANZECC & ARMCANZ

sediment guideline values. The sites (13 and 26) are both located in Zone 3 to the west (Fifth Creek)

and north (towards Whyalla) of Port Pirie respectively and the values reported for Site 13 are

comparable with the background sites at Port Davis (site 19) and Fisherman’s Bay (Site 20).

The other twelve sites reported metal concentrations over the ANZECC/ARMCANZ (2000) guideline

GV-low value with one (site 5) having Pb, Zn, Cd and Ag over the GV-high value and six sites with Pb,

Zn and Cd above the GV-high value (sites 14, 39, 42, 43, 46 and 48).

Site 5, which is within the Port Pirie river adjacent to berths 9 & 10, returned extremely high levels

(above the ANZECC/ARMCANZ (2000) guideline GV-high values for each metal) of Pb, Zn, Cd and Ag.

Levels of As and Cu also returned levels above their respective ANZECC/ARMCANZ (2000) guideline

GV-low values. These high concentrations were found within each size fraction recorded (this site

did not contain sediment >2mm). Zn returned a concentration in the >63-250µm size fraction nearly

ten times the ANZECC/ARMCANZ (2000) guideline GV-high value. The finest fraction of the Site 5

sample also returned a Pb concentration over ten times the guideline GV-high value.

In terms of the metal concentrations within the size fractions, nearly all sites bar one (site 53) had

the highest metal concentrations within the <63µm fraction. However, whilst the smaller size

fraction (<63µm) did contain the highest metal concentrations, when we look at the size fraction

proportions, the bulk of the contamination was still found in the 63 - 250µm size fractions which is in

agreement with previous works (Dossis and Warren, 1980).

27

Site no.

Size fraction Size fraction proportion

Ag mg/kg Al mg/kg As mg/kg Cd mg/kg Co mg/kg Cr mg/kg Cu mg/kg Fe mg/kg Mn mg/kg Ni mg/kg Pb mg/kg Zn mg/kg

5

< 63µm 35.47 19.40 23698.95 51.73 28.53 6.53 24.90 143.91 18299.45 385.84 10.73 3184.24 2831.66

>63 - <250µm 47.40 14.00 14457.44 42.07 26.27 5.33 16.27 135.39 13196.28 305.98 6.73 1913.98 4137.79

>250µm - <2mm 16.03 8.44 11625.59 28.07 15.74 3.87 12.80 74.48 10477.35 278.72 5.27 1501.75 1979.09

>2mm 0

13

< 63µm 1.26 0.01 2740.92 6.04 0.60 0.53 3.14 6.91 1712.32 47.47 1.54 10.51 38.45

>63 - <250µm 9.13 0.01 971.75 3.53 0.20 0.40 3.60 0.77 1076.56 136.72 0.43 4.00 15.26

>250µm - <2mm 81.36 0.01 393.16 3.37 0.10 0.30 2.60 0.60 750.68 148.24 0.30 3.60 12.99

> 2mm 8.25 0.01 88.94 1.57 0.01 0.20 0.40 0.20 171.07 37.79 0.03 1.30 3.37

14

< 63µm 41.23 0.77 22827.31 14.17 13.33 3.51 22.29 27.25 12893.67 197.81 9.21 273.73 568.60

>63 - <250µm 52.39 0.17 6922.91 9.60 7.63 1.47 8.33 7.76 5568.71 117.30 3.10 122.20 309.80

>250µm - <2mm 6.09 0.07 7916.77 12.40 7.47 1.93 9.53 7.43 7386.85 177.56 3.73 148.88 308.59

>2mm 0.00

26

< 63µm 24.91 0.01 11857.93 5.36 1.43 1.57 14.09 9.06 6731.40 86.69 5.40 43.61 98.78

>63 - <250µm 57.43 0.01 2360.18 2.67 0.43 0.50 3.94 1.90 1911.67 40.66 1.13 13.38 27.62

>250µm - <2mm 17.38 0.01 2771.02 3.07 0.43 0.53 4.13 1.67 2120.40 52.47 1.20 14.50 25.40

>2mm 0.00

28

< 63µm 12.97 0.01 14909.39 8.84 6.07 2.05 15.79 12.10 7813.58 115.18 6.52 140.12 311.68

>63 - <250µm 61.09 0.01 1806.02 3.23 2.00 0.40 3.47 2.20 1375.45 66.42 0.92 29.22 76.51

>250µm - <2mm 25.36 0.01 1364.97 4.58 1.47 0.37 2.63 1.78 1207.35 71.35 0.67 28.62 60.08

> 2mm 0.57 0.01 1157.01 2.80 1.05 0.30 1.65 1.85 896.39 31.23 0.50 22.04 50.07

39

< 63µm 27.61 0.93 19532.94 13.16 15.59 3.23 19.56 24.62 11286.90 189.97 7.93 285.86 654.25

>63 - <250µm 55.45 0.01 8466.31 7.50 7.46 1.77 9.43 7.20 6174.81 131.07 3.27 115.50 306.79

28

>250µm - <2mm 16.69 0.01 5391.46 9.67 5.60 1.70 7.43 4.53 6183.19 171.08 2.27 96.91 224.71

>2mm 0.00

42

< 63µm 14.79 0.42 14464.82 14.40 15.78 2.34 14.43 16.93 7444.29 121.94 6.42 223.06 575.39

>63 - <250µm 64.39 0.01 1752.09 5.15 7.61 0.50 3.45 4.05 1325.47 76.90 0.80 64.41 255.64

>250µm - <2mm 14.38 0.01 959.90 5.27 7.33 0.40 2.20 3.48 1109.75 88.09 0.50 71.04 264.91

> 2mm 6.44 0.01 879.73 4.89 2.71 0.41 1.11 2.04 862.06 28.40 0.63 43.10 117.56

43

< 63µm 23.38 0.90 10679.07 20.67 41.22 2.23 11.40 31.31 6775.35 90.80 5.54 278.07 1396.74

>63 - <250µm 53.78 0.10 3999.75 10.40 19.46 1.07 5.70 9.00 3192.29 91.16 2.17 143.74 689.19

>250µm - <2mm 16.66 0.01 2019.01 8.24 12.64 0.77 2.97 5.84 1969.09 64.15 1.23 109.43 506.18

> 2mm 6.17 0.01 2124.42 12.16 10.33 1.03 2.67 5.60 2369.09 31.52 2.33 105.90 386.02

46

< 63µm 9.39 0.80 8839.80 15.17 29.35 2.00 10.27 76.64 5898.99 138.83 4.20 319.05 1063.29

>63 - <250µm 7.00 0.01 1468.48 6.20 8.44 0.63 4.13 6.30 1528.33 133.33 1.10 107.32 324.70

>250µm - <2mm 22.46 0.01 487.24 4.00 4.40 0.30 1.60 4.40 790.98 84.58 0.30 88.28 197.73

>2mm 61.15 0.01 255.62 1.08 0.90 0.20 0.45 1.18 224.24 14.70 0.08 21.10 39.86

48

< 63µm 6.10 1.80 18925.17 27.21 36.24 3.68 17.85 59.50 11671.26 179.33 8.70 595.93 1680.76

>63 - <250µm 36.02 0.02 1458.17 6.27 9.92 0.50 3.07 8.19 1461.91 147.82 0.65 157.63 577.88

>250µm - <2mm 47.93 0.01 979.46 4.59 4.89 0.43 2.26 3.40 1288.82 166.32 0.47 102.60 251.08

> 2mm 9.94 0.01 199.84 1.50 0.60 0.17 0.40 0.80 250.92 21.93 0.10 16.52 36.05

53

< 63µm 41.79 3.10 16611.74 7.03 2.80 2.27 17.66 9.83 9168.16 119.67 6.83 115.41 195.20

>63 - <250µm 41.68 2.23 7388.33 6.83 2.40 1.47 10.17 5.07 6634.61 92.75 3.33 68.46 184.17

>250µm - <2mm 15.20 1.80 9130.11 10.03 2.67 2.10 12.26 4.96 10527.25 139.31 4.26 74.34 240.92

>2mm 0.00

59

< 63µm 23.05 0.33 39463.75 32.57 7.13 14.85 33.27 29.21 26502.00 465.13 21.45 198.46 232.07

>63 - <250µm 30.44 0.23 33751.49 46.62 6.91 16.65 32.24 25.46 27550.37 602.83 21.42 187.42 233.00

>250µm - <2mm 14.73 0.01 8096.93 22.38 3.27 4.94 8.04 6.77 7982.08 391.88 5.07 129.55 112.14

29

> 2mm 31.78 0.01 6031.84 14.90 2.61 2.61 5.39 5.15 4712.46 125.30 3.05 118.49 88.50

61

< 63µm 20.34 0.72 42555.09 12.43 3.70 13.94 41.38 42.85 26712.17 163.63 26.34 172.87 157.47

>63 - <250µm 64.37 0.27 9481.03 3.03 0.80 3.29 10.92 5.32 7495.65 52.68 6.34 27.11 37.93

>250µm - <2mm 10.04 0.22 2587.24 8.02 1.47 3.50 2.90 5.27 2652.49 84.74 3.00 135.67 70.51

> 2mm 5.25 0.01 803.65 3.80 1.93 1.47 0.87 2.70 873.95 39.65 1.30 134.48 66.89

64

< 63µm 5.39 0.01 43410.30 38.18 6.23 13.75 41.36 59.20 29109.31 401.70 19.67 710.97 714.42

>63 - <250µm 37.13 0.01 2618.44 5.75 0.70 0.95 3.55 3.97 2713.16 43.53 1.38 66.16 61.86

>250µm - <2mm 53.70 0.01 1707.38 7.27 0.64 0.86 2.29 2.74 1898.33 77.48 0.74 89.95 52.84

> 2mm 3.78 0.01 1969.27 9.29 0.83 0.87 2.01 5.01 2264.26 51.46 0.80 172.44 74.08

ANZECC/ARMCANZ (2000) sediment GV-low

1

20 1.5 80

65 21 50 200

ANZECC/ARMCANZ (2000) sediment GV-high

4 70 10 370 270 52 220 410

* the ANZECC & ARMCANZ (2000) guidelines set an Environmental Concern Level of 2.3 µg/L for As (III) in marine waters. This figure can be adopted as a marine low reliability trigger value, to be used

only as an indicative interim working level.

^ the ANZECC & ARMCANZ (2000) guidelines give a high reliability marine guideline value for cadmium of 5.5 µg/L calculated using the statistical distribution method with 95% protection. The 99%

protection level is 0.7 µg/L, is recommended for slightly to moderately disturbed ecosystems.

Table 3 - Metal concentrations within size fractions of sub-section of Port Pirie surface sediment samples

30

5 Potential asset recovery value

The metal concentration results indicate that two areas in particular – the Port Pirie river and First

Creek are still extremely contaminated by Pb, Zn, Cd, Cu and As, with the Port Pirie river also

reporting high Ag levels.

Whilst the Port Pirie river mouth and creeks running off the river are also highly contaminated by Pb,

Zn, and Cd, the seagrass and mangrove communities are relatively healthy despite the high sediment

metal levels. The areas that offer the best environmental and asset recovery potential through

remediation are shown in Figure 11. Restricting the sediment removal to the top 1m in these areas

will remove the most highly contaminated sediment in the whole system, will align well with the

dredging requirements for safe shipping at Port Pirie and be contained to areas already

environmentally degraded.

Figure 11 shows the two areas that offer the most concentrated metal contaminated sediments

from the Port Pirie (Port Pirie River and First Creek). In First Creek, the area runs from Site 6.0C to

just seaward of Site 7.0C (approx. 1km) and has a maximum volume of 25,300 m2. The depth of the

likely contamination based on the two cores indicated that top 80cm is the likely extent of the

contamination within First Creek giving a volume of approx. 20,240m3. The proposed Port Pirie river

asset recovery area extends from prior to the creek at the north of the smelter site to the ‘Bridge to

Nowhere’. The area covers a maximum of 767,700 m2 and with the river’s contamination largely

contained to the top 70cm, gives a volume of contaminated material of approx. 537,000 m3.

To calculate the asset recovery potential, several assumptions were made in relation to the asset

recovery areas and the metal concentrations within the sediments. Firstly, the metal concentrations

were calculated using the preliminary results from sites located within the proposed asset recovery

areas (Table 9). The river mouth and wider Zone 1 offer further potential asset recovery zones and

can be included within future works.

Sediment density was calculated for two different sediment densities scenarios of silty inorganic

(min dry density of 1300) and silty/gravel (maximum dry density of 2400).

Ag (mg/kg) Pb (mg/kg) Zn (mg/kg)

First Creek Site 6.0C & 7.0C

Mean (S.d.) 0.6 (0.26) 656.53 (115.39) 657.55 (104.38)

Min 0.09 <0.10 198.77

Max 3.11 1493.00 1600.47

Port Pirie river Sites 1, 4, 5, 64-70, 16.0C, 17.0C & 18.0C

Mean (S.d.) 6.31 (1.74) 2447.36 (542.58) 3355.93 (879.36)

Min 0.10 0.46 36.71

Max 41.84 10588.09 21036.96

Table 4 - Mean, standard deviation, maximum and minimum values for As, Pb and Zn within the Port Pirie river and First Creek asset recovery areas.

31

Figure 10 - Potential First Creek and Port Pirie river asset recovery areas

32

Whilst Ag is the most precious metal that may be recoverable, conservative estimates of

concentration (0.00063% weight) were used in the calculations based on the Pirie river data mean.

Ag has been calculated for a maximum sediment volume of 27,500m3 to account for the smaller

distribution which appears to be contained to the river area directly adjacent to the smelter berth

areas. No inclusion of First Creek sediments has been used for the Ag calculations as concentrations

reported were significantly lower than the river sediments.

The calculations for Pb and Zn, whilst conservative (0.24 and 0.34% weight respectively), are based

upon mean metal concentrations within the river and First Creek of Pb and Zn (to 70cm for the core

data) rather than surface metal concentrations.

Estimated market price was based on current (July 2020) values and included for Pb, Zn and Ag only.

No accounting has been made for the other metals or for potential disposal costs for non-valued

metals (such as As). No examination has been made for rare earth elements (REE) within the current

works but there may be the potential, through the asset recovery and concentration stages, for

recovery of REE.

Volume 557240 m3

Silt, inorganic

Min Dry Dens.

1300 Min Mass 724412 tonnes

Silty/gravel Max Dry Dens.

2400 Max Mass 1337376 tonnes

Min Max

Wt% Pb 0.24 Mass Pb 1739 3210 tonnes

Wt% Zn 0.34 Mass Zn 2463 4547 tonnes Price/tonne Min Max

Total Pb value 1800 $3,129,460 $5,777,464

Total Zn value 2200 $5,418,602 $10,003,572

Table 5 – Potential asset recovery calculations for Pb and Zn

Volume 27,500* m3

Silt, inorganic

Min Dry Dens.

1300 Min Mass 35750 tonnes

Silty/gravel Max Dry Dens.

2400 Max Mass 66000 tonnes

Wt% Ag 0.00063 Mass Ag 724,114 1,336,826

Price/ t.oz Min Max

Total Ag value 18 $13,034,055 $24,062,870

Table 6 - Potential asset recovery calculations for Ag *Calculated as 5% of the Port Pirie metal recovery area

due to its restricted distribution alongside the Smelter berths.

The estimates show a potential value of between $21.5 and 40 million in Pb, Zn and Ag alone that

could be recovered (based on the preliminary distribution mapping). The valuation also does not

include recovery, remediation and concentrating costs.

33

The estimates are conservative and limited to the area of immediate proposed dredging. This work

demonstrated that high level contamination extends into the river mouth and the creeks to the

north of the smelter as well as the areas of intertidal fill opposite the smelter. A more extensive

assessment will need to be made to estimate the total embodied value in the accessible area, along

with an assessment of processability investigations to fully characterise the economic potential of

remediation.

5.1 ALIGNMENT WITH MAINTENANCE DREDGING REQUIREMENTS.

Flinders Ports currently are not able to utilise the shipping channel at Port Pirie to its gazetted

navigational depth of 6.3mCD due to silting up of the channel. Dredging has not been undertaken

due to the contaminated status of the sediments and limited options for the disposal.

Maps provided by Flinders Ports (Figure 11) illustrates the current dredging requirements to take the

channel to the navigational depth. Currently, broad estimates of the lost opportunity to Flinders

Ports is in the range of $4 million per year of shipping capacity not able to be utilised due to reduced

depth. Removal of the contaminated sediments from the Port Pirie river aligns strongly with areas

identified by Flinders Ports as requiring dredging and are also the areas identified as being of the

greatest contamination. This suggests win:win outcomes for asset recovery, increasing productivity

of the port and ecological remediation. .

Table 8 outlines the maintenance dredging requirements in Zone 1, which aligns well with the Port

Pirie asset recovery zone outlined in Section 5. In addition, the removal of the nearly 80cm of

contaminated material from the Port Pirie river allows the opportunity of consideration of a deeper

Port at Port Pirie into the future.

Area Dec depth

(m)

Vol to Clear (in cu

metres)

Area Dec depth (m)

Vol to Clear (in cu

metres)

1 6.4 2796 14 6.4 5966 2 6.4 3175 15 6.4 9 3 6.4 1849 16 6.4 0 4 6.4 3117 INNER 1 6.4 9748 5 6.4 9 INNER 2 6.4 2204 6 6.4 482 BERTH 1 5.3 n/a 7 6.4 23 BERTH 2 8.2 311 8 6.4 0 BERTH 3 6.7 6 9 6.4 2 BERTH 4 4.9 16 10 6.4 11 BERTHS 5 & 6 8.2 78 11 6.4 85 BERTHS 7 & 8 8.3 176 12 6.4 8 BERTHS 9 & 10 8.2 125 13 6.4 3586

TOTAL 33,782

Table 7 - Maintenance dredging requirements by area and volume as supplied by Flinders Ports (2020).

34

Figure 11 - Maintenance dredging area requirements for shipping channel to gazetted navigational depth as identified by Flinders Ports (2020)

35

6 Discussion

This study has demonstrated that the sediments around Port Pirie contain significant levels of metal

contamination, namely Pb, Zn, Cd, Cu, As and Ag, with elevated metal concentrations being recorded

up to 15km away of the smelter. The Port Pirie river, river mouth and First Creek (Zone 1) can be

considered as the epicentre of the metal contamination with the river in particular having extremely

high surface sediment concentrations of Pb, Zn, Cd, Cu, As and Ag that exceeded the

ANZECC/ARMCANZ (2000) guidelines for sediments.

Within the Port Pirie river sites, most exceeded both the ANZECC & ARMCANZ (2000) sediment GV-

low and high for Pb, Zn, Cd and As as well as Cu when Pb/Zn were extremely high (>2000mg/kg).

Sites within the Port Pirie river also reported very high values of Ag. Through discussions with

Nyrstar Port Pirie smelter operators it is thought that the Ag was due to a historic leak from the

precious metals refinery (now gone) which occurred over many years. Whilst the leak was

discovered, and subsequently ‘lost’ silver sands recovered from under the refinery building, the full

extent of the Ag losses from the site were not known. First Creek and sites adjacent to it also

reported nearly all sites with Zn, Pb and Cd over the GV-high. First Creek was slightly different to the

Port Pirie river in that Cu exceedances were fewer.

The depth data (Section 3.2.4), whilst limited to shallow waters only, indicated that the whilst the

contamination is extremely high within Zone 1, it is restricted to the top 60-70cm with the highest

concentrations in the surface layer and decreasing with depth. Geological studies of the Upper

Spencer Gulf estimated sediment accumulation (the rate at which particles settle on top of each

layer) as being between maximum 1 - 2.7mm yr-1 (Belperio et al. 1984). The depth of the elevated

metal concentrations as found within this study over twice as deep as this prediction and it is likely

that the geological calculations do not account for the aerial or effluent sediment deposition from

the smelter, or for the mobilisation of sediments with vessels movements or after dredging and

disturbance.

The extent of the contamination depth found within this work concurs with studies in the Port Pirie

supratidal (Lent et al 1992) where sediments metal levels were at background levels by 60cm. It is

unknown whether vertical migration of lead (as happens within soil matrices) occurs in sediments

but lead and zinc concentrations appear to decrease with depth with the top layers having at least

50% higher concentrations than the deeper layers. This pattern may only be evident in shallow

waters as, Laffrata et al. (2019) found evidence in deeper seagrass beds that the smelter’s influence

could be observed in subtidal sediment cores down to over 1.2m depth. Future research will be

necessary within the deeper areas and seagrass beds to ascertain whether the same patterns form

the shallower areas continue throughout.

Previous studies (Ward, Warren, and Tiller 1984; Ward and Young 1982) concluded the highest

metal concentrations were found at First Creek (the effluent discharge location). Of note however, is

that the majority of previous studies examining First Creek were undertaken prior to 2000. In 2002, a

Process Effluent Treatment System (PETS) was installed through which effluent waters are treated

prior to being discharged. Records from 1994 recorded the annual load discharged into First Creek as

~42 tonnes (t) of lead and 162 t of zinc (unpublished data as reported in Gaylard et al 2011). After

the building of the PETS the metal loading slowly decreased, and the 2016/2017 National Pollutant

Inventory (Australian Government National Pollutant Inventory 2016/2017) reported water

36

emissions as 9.6 tonnes of Pb and 23 tonnes of Zn being discharged to First Creek. The PETS plant

likely explains why within this study the Port Pirie river sites had metal concentrations of Pb, Zn, As,

Cd and Cu far higher than First Creek sites.

Whilst metal contamination was apparent within Zone 2 from Weerona Island to Ward Spit the sites

had intermediate metal concentrations (exceeded the GV-low but not the GV-high) of Pb, Zn and Cd

but were largely contained within the top 20cm and had few exceedances for other metals. Zone 3

sites reported only 4 exceedances (across 22 sites) of the ANZECC & ARMCANZ (2000) sediment GV-

low values. Other than one Cd result at 60-70cm depth at Port Davis (site 20), the cores taken at

Zone 3 sites (sites 19-22) reported no level of metals over ANZECC & ARMCANZ (2000) sediment

guidelines at any depth.

The small study examining metal concentrations within different size fractions indicated that the

highest metal concentrations are held within the <63µm fraction. However, whilst the smaller size

fraction (<63µm) did contain the highest metal concentrations, the bulk of the contamination was

still found in the 63 - 250µm size fractions which agrees with previous works (Dossis and Warren

1980). If analysis of asset recovery potential proceeds these size fraction distributions will be very

important during the hydrodynamic modelling of dredging impacts.

Site Author Maximum trace element concentration mg/kg

Zn Cu Pb As Cd

Lake Illawara (Griffins Bay), NSW Jafari (2009) 350 88 59 - -

Whyalla, SA Harbison (1984) 3240 - 635 - 6

Derwent River, TAS Jones et al. (2003) 22593 1182 3866 657 3866

Cox and Preda 2005 59000 1490 8120 1400 477

Cockle Creek (Lake Macquarie), NSW Roy and Crawford (1984) 6250 420 7050 - -

Port Jackson, NSW Birch and Taylor (1999) 7622 1053 3604 - 243

Thames River, UK Attrill and Thomes (1995) 1050 348 1634 45 10

Mersey Estuary, UK Bryan and Langston (1992) 379 84 124 42 1.1

Restronguet Creek, UK Bryan and Langston (1993) 2281 2398 341 1740 1.5

San Francisco Bay, USA Birch (2000) - 161 67 - 0.5

Port Pirie, SA Current study 21036 491 9166 165 55

Table 8 – Maximum metal concentrations (mg/kg) in surface sediments from industrial and urban marine and coastal systems.

This study concurs with previous works (Cook 1999; Gaylard et al. 2011; Ross 2001; Tiller et al. 1989;

Ward and Young 1981). Whilst it appears initially that there is a decrease in the levels of the

individual contaminants when compared to the historical data (Table 3) levels, it should be noted

that many of the extremely high values (Thomas 1972, Thomas 1987, Lent et al 1992) were recorded

in First Creek at (or close to) the effluent discharge point. No samples were taken in this study from

the discharge point (1M flume) where it enters First Creek. If the First Creek historical data points

are excluded from the dataset, the concentrations recorded within this study are of the same

magnitude as recorded previously. Given that most of the historic data is greater than 30yrs old and

metal concentrations remain of significant ecological concern demonstrates that the Port Pirie river

and First Creek will remain highly contaminated unless active remediation is undertaken.

37

Surface sediment metal concentrations have been compared with metal concentrations from other

industrial and urban estuaries worldwide (Table 5). Whilst limitations exist in making comparisons

between studies, the comparison highlights that Port Pirie is highly contaminated by any standard.

Whilst Port Pirie may not have Cu, As and Cd levels as contaminated as the Derwent River (TAS), the

levels of Zn and Pb are higher than most reported ‘contaminated’ marine sites around the world.

Of greatest concern are the levels of Pb and Cd reported, which are amongst the most toxic of metal

contaminants and are known to induce neurological disorders and multiple organ damage even at

low levels of exposure (Tchounwou et al., 2012). These metals affect aquatic organisms and wildlife

in contact with contaminated sediments, causing a decrease in biodiversity and population size

(Beyer et al., 2004). For example, the impact on lobster, midges, bivalves and amphipods have been

investigated (Besser et al., 2015) with the potential for biomagnification (and consequent human

health risk) since invertebrates are an important food source for wildlife (Beyer et al., 2004).

The seagrasses and mangroves appear healthy and abundant, with a 2017 assessment classifying the

mangroves in localities around Port Pirie in good condition (Stockbridge 2017). Observational data

within First Creek and at the smelter itself during this current work showing some seagrasses and

mangroves in poor condition but the majority of mangroves and seagrasses of the Port Germein

areas appearing to be in good condition even though the sediments had extremely high

concentrations of metals. High concentrations of metals in the mangrove plants themselves

(unpublished data) had little apparent impact upon visual plant health unless directly under the

smelter itself. A recent review of over 23,000 published estimates of trace metal concentrations in

seagrasses highlighted that the zinc levels recorded at Port Pirie in Posidonia australis were the

highest ever recorded in published records (Sánchez-Quiles et al. 2017). Whilst not appearing to

inhibit the plants growth, little research has been undertaken looking at the impacts elevated metal

levels have long term on marine plants.

Whilst impacts may not be observed at an individual plant level, field experiments conducted at Port

Pirie, demonstrated significant metal levels within a variety of species (fish and bivalves) and within

the seston itself (Gaylard et al. 2011; Edwards et al. 2001) and further to this, the community

structure of the marine system is impaired through negative impacts on the growth, biomass and

diversity of epiphytes and associated species that usually feed on the epiphytic assemblages

reported (Ward et al. 1984) with distinct species composition changes in line with metal

contamination concentrations also recorded (Ward and Hutchings 1996).

It has been estimated that the subtidal sediment areas of Germein Bay (approx. 20km2) contain at

least 25,000 tonnes each of lead and zinc and 500 tonnes of cadmium and arsenic (Tiller et al. 1989).

This studies initial calculations, based on conservative estimates, of Pb and Zn within the Port Pirie

and First Creek river asset recovery areas alone were 3200 tonnes of Pb and 4500 tonnes of Zn

indicates that the previous studies grossly underestimated the levels. The sediments of Port Pirie

(and particularly within Zone 1) continue to have some of the highest Pb and Zn levels reported in

the world (Table 12). Without removal, the sediments within the Port Pirie river will continue to

have long-term chronic and deleterious effects upon the wider Germein Bay and Upper Spencer

Gulf.

Most legislation (such as the Commonwealth Environment Protection (Sea Dumping) Act (1981) in

Australia) are based on the assumption that the ‘no-action’ option in relation to metal

contamination will result in lesser environmental harm, as metal contaminated sediments will be a

38

lesser risk if undisturbed and in-situ. However, many contaminated sediments are within areas

where industrial processes have polluted the systems. As such, they are within areas with ongoing

industries and may be subject to daily disturbance through boat movements and potential

maintenance and/or capitol dredging. These sediments are a continued risk to the environment, and

in some cases the contaminated material is not safely ‘locked away’. Precipitation of dissolved

metals or conversion to more strongly-complexed metals does not readily occur within the Port Pirie

sediments, and the majority of metals are in the dissolved, and likely bio-available, phase (Ferguson

1983, Gaylard et al. 2011). As such it is likely the metals are being transported through the deep-

water shipping channel, explaining why sites within adjacent mangrove creeks and seagrass areas

have high concentrations of metals within them.

Even within sediments and soils where the metals and metalloids are more tightly bound and hence

less bio-available, which is not the case at Port Pirie (Gaylard et al. 2011), there exists the potential

for these metals to once again become biologically available through changes in conditions such as

pH, temperature and oxygen status of the system. Lab-based experiments on metal contaminated

sediments investigating CO2 induced acidification effects (as predicted under current climate change

modelling) showed that decreasing pH led to increased metal solubility (Wang et al., 2015), with

changes in seawater pH potentially enhancing metal transfer from solid matrices to the liquid phase.

As such, metal concentration in the seawater column may reach undesirable levels at a local scale

producing serious negative effects in dynamic coastal systems (Khosrovyan and Riba, 2014). Given

that the metals are considered as bio-available currently at Port Pirie, any increase in the bio-

availability would only increase deleterious effects on the marine system further.

The remediation of metals/metalloids brings considerable challenges since these elements, given

their chemical properties, can never be degraded but only stabilized (Marques, 2016). The current

gap between lab-based experiments and ‘real-life’ situations which have multiple stressors,

influences and field conditions is difficult. Even when remediation is undertaken (by whatever

means), small scale remediation projects may reduce contaminant loading for a small period of time,

however; if the larger system is still containing contaminants then it is likely that inlets and areas

where fine sediments accumulate will eventually become sinks for the contamination again

(Marasinghe Wadige et al., 2016). This was demonstrated by Birch et al. (2015) who looked at the

effectiveness of remediation at a lead-contaminated former industrial site and reported that the

lead, zinc, copper and nickel contamination levels had nearly returned to pre-remediation levels

after 6 years.

This work assessed the current contamination status of the shallow sediments surrounding Port Pirie

and demonstrated high levels of Pb, Zn and Cd extend up to 15km from the smelter. Two areas in

particular – the Port Pirie river (and mouth) and First Creek are still extremely contaminated by Pb,

Zn, Cd, Cu and As, with the Port Pirie river also reporting high Ag levels. The estimates show a

potential conservative asset value of between $21.5 and 40 million in Pb, Zn and Ag if recovered

(based on the preliminary distribution mapping). Whilst more extensive assessments will be

required, the economic potential of the asset recovery requires detailed consideration.

Contaminants at levels such as those at Port Pirie have chronic effects on individual species which

drive community and ecosystem impacts and reduce ecosystem services. The marine sediment and

waters of Port Pirie are significantly contaminated with Zone 1 in particular demonstrating levels of

Pb, Zn and Cd far in excess of levels known to impact ecosystem health. Habitat forming species such

as mangroves, seagrasses and bivalves, all of which are found at Port Pirie, provide ecosystem

39

services such as coastal protection, provision of food from fisheries, regulating our climate through

carbon sequestration and treating our wastes (Gaylard et al 2020). Toxicants alter functioning of

marine systems by increasing respiration and reducing overall productivity (Johnston & Mayer-Pinto

2015), as well as affecting habitat quality which can then change species occupancy (Mariani &

Alcoverro 1999). Metal contamination decreases species diversity, changes community structure,

results in abundances and biomass decline leading to reduced marine resource yields and

degradation of habitats (Islam & Tanaka 2004, Mayer-Pinto et al. 2020).

Currently the shipping harbor in Port Pirie is under-utilised as siltation has resulted in only shallow

draft vessels being able to be used under tidal restrictions. The significant metal contamination of

the sediments would result in extreme spoil disposal costs meaning dredging has been cost

prohibitive. Metal recovery from dredged sediments may offset the cost of disposal of sediments

taking the cost of a dredge program from prohibitive to attractive. Further to this, there are

numerous benefits to the environment and social outcomes rom remediation of Port Pirie sediments

with opportunities for recovering social licence from the local and regional communities.

In addition to the potential asset recovery and major benefits in the diversification and growth of the

existing Port, the remediation of the highly contaminated Port Pirie marine system would directly

benefit the wider Upper Spencer Gulf ecosystem and communities.

40

7 Conclusion

Re-imagining metal contaminated sediments as potential asset repositories could fundamentally

change how we manage and remediate polluted systems. It may be that the recovery of metals such

as Pb and Zn are not cost-effective in themselves, but the presence of Ag within the Port Pirie river,

and other metals such as Al may provide sufficient returns to be cost-effective. Utilisation of existing

processing plant has been identified as a major cost-effective way of recovering assets (Andrew and

Nairn, 2013). The potential to use Nyrstar Port Pirie smelter technologies in the recovery of the

metals could reduce the processing costs associated.

Many of our coastal and marine environments bear the legacy of our industrial past with extremely

high levels of metal contamination within the sediments and associated flora and fauna. Ultimately,

the degraded and contaminated status of the Port Pirie marine environment will not change without

action. Currently the potential for diversification of Port Pirie from a smelter focused city to a multi-

user Port with industrial, recreational and tourism interests is limited by the high levels of

contamination. Altering the way that contaminated systems are managed and re-imagining the

contamination as an asset recovery has the potential to encourage the clean-up of pollution legacies

leading to better outcomes, more efficient industry practices and new opportunities.

7.1 WAY FORWARD

Further works will be required to refine the metal distribution mapping to include dynamic

processes that influence the fate of metals in the Port Pirie marine ecosystem such as rates of

sediment resuspension and mapping/optimisation of smelter processes or alternative technologies

for asset recovery. Key to future works will be the alignment of the asset recovery footprint with

maintenance dredging and environmental remediation requirements. This will offer economic metal

recovery value, reduced burden of legacy pollution impacting the marine environment and the safe

operation, thereby re-opening the opportunity for expansion of the Port to the current gazetted

depth. Opportunities exist for multiple stakeholders to work co-operatively and see an improved

Port Pirie marine environment in terms of environmental, social and economic outcomes, promoting

commitment to being responsible users of the marine environment.

Recommendations for the future stages include:

• Extension of the asset maps (through sample collection and analysis) through the deeper Port

Pirie river, shipping channel and surrounding areas to allow completion of the modelling of the

likely asset recovery value. This extension of the asset map will also collect sufficient information

to inform Port dredge licensing requirements. Alignment of optimal metal recovery areas with

dredge requirements.

• Exploration of recovery / remediation options including emerging technologies along with trial

reprocessing experiments and stages of upgrading and subsequent concentrate production (in

conjunction with Nyrstar and research institutes).

• Evaluation of the mineralogical and sediment particle size distribution of the valuable metals.

This information assists both the economic assessment and selection of appropriate value

extraction strategies/technologies.

• Mapping/overlay of geochemical and particle size data across contaminated areas and

generation of 3D models for visualisation and spatial characterisation of the potential resource.

41

• Identification of remediation / recovery techniques – this will include n.

• Trials of key techniques with calculation of recovery rates, grade of concentrate and, critically,

metal levels remaining in tailings streams.

• Recommended options with triple bottom line and cost-benefit analysis.

42

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50

Appendix A – Site location and observational data

Site no. Method Date X Y Water depth

Notes Habitat

1 Grab 31.10.18 138.01579 -33.1649 -1.3 Fine silty sand with shell gravel. Silty sand / mud

4 Grab 31.10.18 138.01497 -33.1766 -6.3 Thick mud with anoxic layer close to surface. No obvious biology. Mud

5 Grab 31.10.18 138.015 -33.1672 -7.6 Mud with non-smelly anoxic layer very close to the surface. No evidence of biology. Mud

7 Grab 29.10.18 137.96 -33.1014 -5 Bare substrate with Heterozostera shoots, evidence of bioturbation Seagrass

8 Grab 29.10.18 137.966 -33.0919 -4.8 Muddy sand, Zostera, red algae, tubeworms Seagrass

9 Grab 29.10.18 137.95 -33.0901 -4.8 Muddy, obvious polychaetes Mud

10 Grab 30.10.18 137.879 -33.0951 -8.6 Sandy silty mud - lots of shell fragments and no vegetation Silty sand / mud

11 Grab 31.10.18 138.033 -33.0661 -1.1 Sand, no obvious fauna, Layer change at 1.5cm Silty sand / mud

12 Grab 29.10.18 137.963 -33.077 -5.7 Sandy anoxic layer mud - smelly Silty sand / mud

13 Grab 01.11.18 137.88658 -33.1759 -1.4 Sand area with fringing seagrass at mouth of tributary. Seagrass

14 Grab 29.10.18 137.977 -33.0802 -5.5 Sandy mud - very fine, bit anoxic, fibrous stuff in mud, no biology Silty sand / mud

15 Grab 31.10.18 138.013 -33.0456 -1.5 Bare sand area, muddy sand with very smelly anoxic layer at ~1.5cm Silty sand / mud

16 Grab 01.11.18 137.89708 -33.1879 -2.1 Upper mangrove tributary. Clay / fine sandy clay. Some shell debris. Mangroves

18 Grab 30.10.18 138.0468 -33.1246 -4 Cobbly mixed substrate. Patchy Posidonia australis, strong current, tributary mangrove lined. Seagrass

19 Grab 30.10.18 138.03705 -33.1076 -1.3 Grab taken in shallows. Sandy top layer, siltier deeper with some shell gravel. No biology obvious. Silty sand / mud

20 Grab 29.10.18 138.01 -33.1424 -1.5 Seagrass bed - silty, anoxic and dark, seagrass and rhizomes, shells Seagrass

21 Grab 31.10.18 138.017 -33.1324 -1.5 Seagrass bed. Sample taken in bare sediment mud amongst Posidonia australis. Very fine layer above anoxic mud with dense rhizomes - very smelly.

Seagrass

22 Grab 31.10.18 137.921 -33.0147 -1.6 Shelly sand with patchy brown algal mosaic. Algae

23 Grab 31.10.18 137.952 -33.0135 -1.6 Shell gravel with sand. Composite of two grabs. Sandy gravel

24 Grab 01.11.18 137.913 -33.1688 -3.3 Tributary mouth. Sandy shell gravel - very fine shell. Sandy gravel

25 Grab 30.10.18 137.891 -33.1282 -4 Seagrass bed - dense patchy Amphibolas antarctica? With Posidonia and other biota present (razorfish) Seagrass

26 Grab 30.10.18 137.831 -33.0559 -9.3 Muddy sand, faint evidence of anoxic smell, some anoxic layering. Few holes / bioturbation but no animals.

Silty sand / mud

27 Grab 30.10.18 137.883 -33.053 -15.9 Deeper channel area. Firm sandy mud, little smell, stalked bryozoans and colonial ascidian. Silty sand / mud

28 Grab 31.10.18 137.941 -33.1119 -5.5 Muddy silty sand. Little obvious biota, few hair like fibres. Anoxic layer change at 2cm. Silty sand / mud

29 Grab 30.10.18 137.918 -33.0632 -5.6 Shell gravel amongst silty sand. Small amount of Heterozostera with red/brown algae. Seagrass / algae

30 Grab 30.10.18 137.884 -33.007 -8.5 Seagrass bed - muddy sand with dense Heterozostera sp. Seagrass

31 Grab 30.10.18 137.864 -33.1554 -2.9 Seagrass bed - dense patchy Posidonia australis and maybe Spinulosa. Substrate sandy shell grit. Seagrass

33 Grab 30.10.18 137.887 -33.0753 -6.9 Seagrass bed - Zostera with muddy substrate, some shell fragments, live bivalves. Seagrass

34 Grab 31.10.18 137.928 -33.0736 -2.3 Seagrass bed. Mosaic Amphibolas and Posidonia with shell gravelly sand substrate. Seagrass

35 Grab 30.10.18 137.851 -33.0937 -6.4 Posidonia, shelly fine grit and sand. Little sediment sample as lots of large shell pieces. Seagrass

36 Grab 30.10.18 137.84 -33.0222 -7.8 Seagrass bed - partial sample with seagrass and small amount of sandy mud sediment Seagrass

37 Grab 30.10.18 137.961 -33.0359 -8.8 Seagrass bed - fine sandy silt with obvious anoxic layer and small smell. Halophila roots and plants present

Seagrass

39 Grab 29.10.18 137.98 -33.0871 -5.7 Muddy sand, no veg, few hydroids, dead seagrass leaves, a little anoxic Silty sand / mud

40 Grab 29.10.18 137.99 -33.0927 -4.8 Sandy mud, Heterozostera shoots, red algae, some shell gravel Seagrass

42 Grab 01.11.18 137.953 -33.1216 -4.4 Seagrass bed. Posidonia australis over muddy sandy silt. Seagrass

51

43 Grab 01.11.18 137.95 -33.1411 -1.7 Seagrass bed. Sandy muddy silt overlaid by Posidonia augustifolia and fibrous, sinuous mat. Seagrass

44 Grab 01.11.18 137.981 -33.1347 -1.2 Seagrass bed. Posidonia australis, bryozoans, amphipods over sandy mud. Seagrass

45 Grab 01.11.18 137.985 -33.1219 -1.3 Seagrass bed. Posidonia australis over sandy silty mud. Seagrass

46 Grab 01.11.18 138.001 -33.125 -1.4 Large shell gravel mixed sandy/mud substrate. Sandy gravel

47 Grab 31.10.18 138.019 -33.0986 -1.8 Seagrass bed - partial sample over dense Posidonia Seagrass

48 Grab 30.10.18 138.04 -33.1288 -1.4 Bare area - no seagrass, silty gravel, shells. No obvious fauna, slight anoxia. Sandy gravel

49 Grab 30.10.18 138.05047 -33.1127 -0.5 Mangrove site - Sample taken amongst mangrove roots in adjacent bank by bucket/WN Mangroves

50 Grab 31.10.18 137.97974 -33.0226 -1 Mangrove habitat. Sand between inside edge of mangroves. Sand substrate with shell gravel (fine). Anoxic layer from ~1-2cm deep.

Mangroves

51 Grab 31.10.18 137.87909 -33.0313 -1.5 Sand substrate amongst mosaic patchy seagrass. Some Heterozostera. Shelly sand. Old detritus under surface sediment (looks like on top of a dead Posidonia bed)

Seagrass

52 Grab 31.10.18 137.92 -33.0342 -6.9 Brown algae / red algae on refusal drops. Successful drop composed of fine shelly gravel/sand and some Heterozostera.

Seagrass / algae

53 Grab 31.10.18 137.94675 -33.0481 -12.3 Deep sample sandy mud with obvious layer change at approx. 2cm. Calcareous tubeworms, diatom mat. Silty sand / mud

54 Grab 31.10.18 138.01276 -33.1246 -1.3 Stromatolite land. Hummocks of raised platforms of mud through sandy mud substrate. Probable dead seagrass bed as organic fibres throughout subsurface 10cm (i.e. below top 2cm). Very smelly anoxic (worst smell of survey) below top 2cm. Mud - fine.

Silty sand / mud

55 Grab 31.10.18 137.99479 -33.0602 -7.3 Mud with diatom layer, stinky anoxic banding from very close to surface (<0.5cm) Silty sand / mud

56 Grab 31.10.18 137.90801 -33.0925 -5.5 Sand - no obvious anoxic layer. Nothing else to note. Silty sand / mud

57 Grab 31.10.18 137.9954 -33.0768 -3.8 Seagrass bed - patchy Posidonia with sandy silty shell gravel sand/silt. Seagrass

58 Grab 01.11.18 138.01919 -33.1547 -1.9 Mouth of Magazine Creek tributary (from Navigation creek). Shell gravel with sand. Layer change at ~1cm to anoxic dark grey shell/gravel sandy mud.

Sandy gravel

59 Grab 01.11.18 138.03389 -33.1562 -1.4 Layer of shell gravel over muddy sand with Heterozostera shoots. Amphipods present. No odour but noticeable layer change at ~1cm.

Silty sand / mud

60 Grab 01.11.18 138.04096 -33.1523 -1.3 Brachiodentic bivalves. Very coarse shell grit. Amphipods present. Mussel beds on run into inner tributary.

Sandy gravel

61 Grab 02.11.18 138.00559 -33.1578 -1.8 Derelict bridge creek - sample taken in the inner fork of the mangrove creek system. Smelter stockpiles within sight. Muddy clay - very red / brown (unlike any seen previously). Shell gravel detritus present. No smell and no evidence of anoxic layer.

Muddy clay

62 Grab 02.11.18 138.00764 -33.1585 -2 Between inner and outer tributary samples. Sandy mud/clay with shelly gravel. No smell, live bivalves. Silty sand / mud

63 Grab 02.11.18 138.01218 -33.1579 -2 Outer entrance to Derelict bridge creek, just on outer edge of pilings (between the two sets of piles). Muddy shelly silt, live bivalves (Katelycia?). Layer change apparent turning from dark brown to grey / black more anoxic layer ~2cm surface

Silty sand / mud

64 Grab 01.11.18 138.016 -33.1769 0 Back edge of mangroves opp smelter on horseshoe bay that people swim in. Sand substrate - possibly next to fill area.

Silty sand / mud

65 Grab 01.11.18 138.0143 -33.1725 0 Edge of mangroves opposite smelter down from boat pier. Heavy muddy clay. Muddy clay

66 Grab 22.08.19 138.015 -33.1672 -7 Revisiting original site 5 Mud

67 Grab 22.08.19 138.01401 -33.1702 -7.2 200m upstream from Site 66 Mud

68 Grab 22.08.19 138.015 -33.1671 -7.2 200m downstream from Site 66 Mud

69 Grab 22.08.19 138.015 -33.1647 -7.5 100 m across river from Site 66 Mud

70 Grab 22.08.19 138.01401 -33.1607 -6.5 Grab taken from side of barge wreck Silty sand / mud

1 C Core 19.08.19 138.01401 -33.1551 0 Offshore of mangroves. Very shelly at the top 2 horizons, matted rhizomes in middle section (apparent throughout the core in smaller numbers). Gloopy sticky mud in top layer.

Silty sand / mud

52

2 C Core 19.08.19 138.009 -33.1447 0 Sticky top layer, some shells throughout. Again, very seagrass root driven. More of an anoxic smell than site 1. Seagrass (patchy mosaics obvious at site)

Seagrass

3 C Core 21.08.19 138.013 -33.1393 0 Soft mud on top, sandy silty below Silty sand / mud

4 C Core 20.08.19 138.023 -33.1308 0 Sand, Posidonia australis, 100% Hinksia sp. Seagrass

5 C Core 20.08.19 137.992 -33.1171 0 Silty sandy and smelly. Lots of gloop Silty sand / mud

6 C Core 21.08.19 137.978 -33.1505 0 Site 6 C (and to a lesser extent site 7 C) from First Creek inner were markedly different to all other sites in terms of colour and composition. Gloop over shell gravel/ silt. Obvious colour change from top gloop to yell/orange shell band (coarse and large shell pieces) and then down to sandy orangey and sticky clay shift (with different colour again).

Silty sand / mud

7 C Core 21.08.19 137.97301 -33.1444 0 See Site 6 C comments. No colour band apparent (as had 6.0C) Silty sand / mud

8 C Core 20.08.19 137.961 -33.1532 0 Shelly sandy top 5cm, fine slightly anoxic below Sandy gravel

9 C Core 20.08.19 137.92101 -33.1639 0 Bare, fine sediment, Hinksia (10-20%), mosaic Zostera nearby Seagrass / algae

10 C Core 20.08.19 138.017 -33.1271 0 Sand over gloop Silty sand / mud

11 C Core 21.08.19 137.94 -33.1381 0 Soft muddy top layer, harder with depth Silty sand / mud

12 C Core 21.08.19 138.00301 -33.0947 0 Sandy, gravelly, silty Sandy gravel

13 C Core 21.08.19 137.98199 -33.1205 0 Fine silty sand Silty sand / mud

14 C Core 21.08.19 138.007 -33.1213 0 Fine silt Silty sand / mud

15 C Core 21.08.19 138.026 -33.117 0 Posidonia australis, 60-70% Hinksia sp. Seagrass

16 C Core 25.09.19 138.0135 -33.1641 0 Smelter north of arsenic dams. Mangroves in poor condition with obvious leaf spots, yellowing and curling. Bud areas appeared to be 'burnt' looking and trees not fruiting

Mangroves

17 C Core 25.09.19 138.0239 -33.1814 0 Solomontown beach. Mangroves area. Strange white colour to water in core tube. Mangroves

18 C Core 25.09.19 138.0147 -33.1719 0 Opposite smelter over John Pirie Bridge (Bridge to Nowhere). Mangroves

19 C Core 26.09.19 137.9464 -33.554 0 Port Broughton. Mangrove lined. Many algal species and seagrass wrack under mangroves. Shell and gravelly substrate. Oodles of amphipods under the wrack.

Mangroves

20 C Core 26.09.19 137.8505 -33.2643 0 Port Davis. No compaction as very thick clay layer close to surface. Mangrove site with undercutting and erosion, slumping of mangrove bank.

Mangroves

21 C Core 26.09.19 137.9835 -33.0208 0 Port Germein. Mangrove area, mangrove sample taken on an island in creek channel Mangroves

22 C Core 26.09.19 138.0337 -33.107 0 Weerona Island. Sandy shell area between mangroves and seagrass evidence of bioturbation. Sandy gravel

Samph 1 Grab 15.05.19 137.97045 -33.152043

0 Samphire habitat north of smelter Samphire

Samph 2 Grab 15.05.19 137.97306 -33.154423

0 Samphire habitat north of smelter Samphire

Samph 3 Grab 15.05.19 137.97885 -33.16134 0 Samphire habitat north of smelter Samphire

Samph 4 Grab 15.05.19 137.980483 -33.163227

0 Samphire habitat north of smelter Samphire

Samph 5 Grab 15.05.19 137.983351 -33.166694

0 Samphire habitat north of smelter Samphire

Samph 6 Grab 15.05.19 137.988186 -33.172497

0 Samphire habitat north of smelter Samphire

Appendix table A- Site number, date sampled, location and site description including main habitat type.

53

Appendix B Water Quality Results

Site WQ As_ug/L WQ Cd_ug/L WQ Cu_ug/L WQ Pb_ug/L WQ Zn_ug/L *

ANZECC & ARMCANZ 95% Level of species protection

4.5* 5.5 1.3 4.4 5.2

ANZECC & ARMCANZ 80% Level of species protection

- 36 8 12 16

1 3.3 2.3 2.1 23.5 87.9

4 3.9 1.9 0.9 36.2 83.0

5 4.5 1.6 2.4 17.5 47.1

6 2.6 0.8 11.1 3.9 15.2

7 2.5 0.6 1.4 3.9 22.8

8 2.8 0.9 1.8 6.0 22.2

9 2.9 0.9 1.9 6.6 20.2

10 2.6 0.2 0.1 0.8 12.1

11 3.9 0.6 1.9 2.8 9.5

12 3.3 1.0 1.0 3.1 15.1

13 3.4 0.6 1.6 3.0 16.1

14 3.2 0.7 1.5 4.7 26.6

15 2.2 0.9 1.3 2.4 16.8

16 2.8 0.1 0.5 1.0 22.4

18 3.4 0.3 0.6 4.2 35.0

19 3.1 0.7 1.6 4.0 22.7

20 5.9 2.0 3.5 43.1 44.8

21 3.7 0.5 0.4 7.9 30.1

22 2.2 0.8 1.1 2.1 6.2

23 2.1 0.3 0.9 2.1 5.2

24 2.6 0.4 0.8 1.5 14.7

25 3.6 0.8 1.6 2.4 10.4

26 2.5 0.5 1.0 2.6 6.4

27 2.7 0.2 0.6 1.5 34.5

28 2.3 0.7 1.0 3.5 13.8

29 2.6 1.0 0.8 2.8 8.6

30 2.3 0.6 1.0 2.2 7.5

31 2.1 0.6 1.0 2.2 8.6

32 2.5 1.0 1.4 2.2 7.3

33 2.5 0.6 1.0 2.2 8.0

34 2.5 0.4 0.7 1.7 17.6

35 2.8 0.8 1.5 2.5 11.4

36 2.4 0.3 0.8 1.7 19.0

37 2.3 0.3 5.2 0.6 10.2

38 2.1 0.1 1.0 0.9 29.6

39 3.0 0.7 1.7 5.5 28.1

40 3.0 0.6 1.8 4.8 26.6

41 3.2 0.9 0.9 3.4 13.1

42 2.4 1.2 1.3 4.1 16.4

43 3.1 0.8 0.6 5.2 53.4

44 3.4 0.7 1.6 14.0 30.6

45 3.4 0.7 15.6 5.2 17.2

46 3.5 0.9 1.8 7.1 31.6

47 3.1 0.9 1.4 3.9 24.2

48 3.7 0.5 <0.1 3.9 21.7

49 3.7 0.7 1.7 7.5 28.2

50 3.4 1.2 1.0 7.9 27.2

X1 2.9 0.9 0.8 4.1 19.9

X2 3.3 0.9 1.5 2.5 8.1

X3 2.2 0.7 1.0 2.6 5.3

X4 3.0 0.8 0.8 2.7 6.4

X5 1.8 0.3 0.3 0.8 22.6

54

X5.1 (same as X5) 2.2 0.5 1.6 2.7 8.5

X6 4.1 1.0 1.8 8.3 27.2

X7 2.2 0.6 0.8 2.3 6.7

X8 2.7 0.6 50.2 2.7 7.5

X9 2.5 0.8 0.9 2.8 9.3

X10 3.6 0.4 0.3 9.5 34.6

X11 3.6 1.2 1.8 13.0 46.4

X12 4.5 1.7 2.1 16.1 62.7

X13 2.1 0.8 0.9 2.5 9.5

Appendix table B - Metal concentration results in water samples

.* The ANZECC & ARMCANZ (2000) guidelines state that there were insufficient data to derive a reliable marine trigger value. A low reliability marine guideline trigger value of 4.5 µg/L for As (V) which is used only as an indicative working level. # Zn GV’s based upon 2020 updated species protection values.

55

Appendix C – Metal concentrations in surface sediments

Total Metals (mg/kg) Carbon Nitrogen Sulphur Particle Size Analysis

Site no. Ag mg/kg

Al mg/kg As mg/kg

Cd mg/kg

Co mg/kg

Cr mg/kg

Cu mg/kg

Fe mg/kg Mn mg/kg

Ni mg/kg

Pb mg/kg

Sb mg/kg

Zn mg/kg N % C% S % % <10 µm

% >10 < 35 µm

% >35 and < 200 µm

% >200 and <2000 µm

ANZECC & ARMCANZ (2000) sediment GV-low

1

20 1.5 80 65 21 50 200

ANZECC & ARMCANZ (2000) sediment GV-high

4 70 10 370 270 52 220 410

1

6304.44 10.52 11.50 1.26 6.69 34.38 6319.80 144.17 2.64 580.27 0.10 918.81 0.24 1.47 8.94 33.77 35.51 27.27 3.44

4

21709.85 34.18 23.95 5.39 20.56 115.01 20224.95 367.19 8.92 2167.70 0.10 3257.80 0.34 1.87 8.74 36.64 37.07 24.15 2.14

5 41.84 18631.10 37.30 25.82 4.99 18.56 119.82 18742.71 396.25 8.30 2602.83 0.10 3282.50 0.34 1.88 7.56 32.14 34.48 31.56 1.83

7

5104.04 3.63 3.79 0.69 6.25 4.90 4620.08 106.09 2.29 80.05 0.10 155.99 0.16 1.91 5.63 24.60 23.91 43.33 8.16

8

6856.45 2.70 5.69 1.00 7.75 6.90 5914.00 132.09 3.03 119.98 0.10 224.16 0.29 3.05 8.86 23.46 29.04 42.48 5.01

9

4983.03 0.44 2.49 0.55 6.16 4.35 4111.02 92.33 2.20 63.14 0.10 109.71 0.26 1.38 8.44 19.55 18.66 44.34 17.45

10

945.93 0.10 0.58 0.06 1.36 1.22 1293.42 26.17 0.52 9.53 0.10 18.25 0.19 4.10 9.81 19.74 20.20 35.47 24.59

11

861.13 0.44 0.65 0.11 1.83 1.78 804.55 41.03 0.57 25.10 0.10 27.49 0.16 1.89 15.50 0.03 1.32 41.89 56.77

12

10598.73 3.94 5.37 1.19 10.93 8.58 8070.76 128.35 4.43 132.16 0.10 240.94 0.32 2.04 9.66 35.69 33.95 27.32 3.04

13 0.04 516.86 0.09 0.41 0.20 2.42 2.29 997.29 170.06 0.32 6.16 0.10 16.85 0.11 0.93 6.72 1.04 2.01 8.68 88.26

14 1.01 11764.74 3.26 8.82 1.49 11.68 11.14 8946.63 153.03 4.80 174.58 0.10 364.50 0.33 2.28 7.41 36.83 30.67 28.71 3.78

15

1513.40 0.50 1.11 0.20 2.72 2.02 1418.66 59.95 0.98 22.85 0.10 50.99 0.13 0.31 7.42 0.00 0.12 49.58 50.30

16

4018.69 0.10 0.41 1.10 5.26 3.54 3389.89 114.16 2.36 3.03 0.10 10.04 0.23 1.89 7.62 33.11 32.68 32.17 2.04

18 0.45 2324.91 0.51 0.71 1.42 2.36 2.57 2451.13 125.68 1.24 19.16 0.10 27.84 0.08 5.06 9.63

19

1160.37 0.10 1.66 0.13 2.14 2.48 962.44 72.41 0.51 47.48 0.10 83.91 0.02 0.49 4.38 5.94 8.15 36.90 49.01

20

7185.77 4.44 20.44 1.22 7.14 15.52 5825.49 134.53 2.81 310.34 0.10 743.48 0.31 2.79 14.40 24.37 27.52 41.30 6.81

21

11453.61 9.31 25.63 2.31 11.38 23.04 9855.84 169.39 5.17 453.64 0.10 943.31 0.48 5.06 7.90 29.46 34.37 33.53 2.63

22

435.04 0.10 0.15 0.07 0.76 0.79 452.99 7.05 0.24 4.77 0.10 6.39 0.15 1.11 12.90 1.40 2.01 13.45 83.13

23

118.34 0.10 0.09 0.00 0.32 0.83 203.37 9.79 0.13 3.81 0.10 5.50 0.23 4.45 17.90 0.85 1.88 26.50 70.77

24

629.69 3.73 0.67 0.58 1.09 0.01 1135.65 108.00 0.64 0.10 0.10 29.37 0.13 4.74 5.91 9.00 11.89 20.64 58.47

56

25

855.92 0.33 0.87 0.43 1.96 0.01 857.15 86.30 0.56 6.10 0.10 42.65 0.30 7.24 8.89 1.67 2.76 35.61 59.96

26 0.03 5299.04 0.10 0.48 0.93 5.86 0.01 3744.95 71.90 2.47 20.58 0.10 48.39 0.30 1.76 7.45 24.18 20.96 43.07 11.79

27

7510.69 2.23 0.78 1.30 8.19 0.05 6073.76 85.13 3.34 58.57 0.10 92.33 0.25 1.68 7.05 30.44 24.83 26.66 18.07

28 0.04 2902.74 1.00 2.22 0.70 3.23 0.01 2108.74 81.46 1.42 40.52 0.10 103.38 0.22 1.24 7.95 15.00 13.76 41.45 29.78

29

2986.61 4.19 0.84 0.72 3.37 0.01 2457.58 71.93 1.33 29.03 0.10 58.86 0.38 2.27 5.61 17.28 17.45 38.06 27.20

30

7174.56 0.40 0.55 0.98 7.34 0.01 4397.12 68.31 3.21 23.57 0.10 57.41 0.31 2.15 7.48 29.42 29.36 36.31 4.91

31

643.80 0.18 0.49 0.47 1.68 0.01 628.93 89.00 0.52 0.93 0.10 27.44 0.11 0.78 6.31 3.17 5.42 43.72 47.69

33

5213.19 1.05 0.73 0.96 5.81 0.22 3739.42 79.51 2.42 35.21 0.10 71.03 0.45 10.46 0.06 23.98 22.44 33.85 19.73

34

1714.85 0.10 0.67 0.62 1.07 0.01 1232.55 49.10 1.01 31.95 0.10 61.69 0.35 4.57 3.76

35

1122.01 0.10 0.19 0.51 1.09 0.01 1184.33 48.57 0.68 3.70 0.10 22.62 0.21 5.25 9.54 8.28 6.69 38.78 46.25

36

940.05 0.10 0.44 0.48 0.84 0.01 837.22 42.18 0.60 3.81 0.10 47.45 0.34 5.60 8.50

37

9311.91 4.91 1.34 1.45 10.82 2.24 7458.59 100.29 4.99 63.85 0.10 124.01 0.67 3.34 21.20 27.14 30.96 35.30 6.59

39 0.95 10572.03 39.24 3.32 0.01 0.01 28.68 9018.21 230.88 9.58 179.05 9.18 457.11 0.26 1.77 6.97 23.15 22.24 39.35 15.26

40

4864.76 9.96 5.18 1.52 5.85 1.84 4795.91 228.18 2.32 124.42 0.10 260.23 0.21 1.66 5.95 18.82 18.94 30.46 31.79

42 0.45 2850.87 3.85 9.22 0.89 3.48 1.90 2265.89 95.70 1.61 94.28 0.10 330.03 0.19 2.26 7.13 17.46 17.18 45.52 19.84

43 1.02 4792.63 12.44 26.07 1.50 5.36 7.89 4161.58 97.88 2.93 196.26 0.10 959.47 0.29 5.86 4.97 18.53 24.95 42.07 14.45

44

10806.12 57.40 55.38 0.01 0.01 57.70 8222.74 263.55 12.00 663.70 17.67 2289.40 0.70 8.76 9.45 27.99 33.34 33.05 5.61

45

10500.19 45.26 35.65 0.01 0.01 47.83 7213.44 183.23 11.16 464.82 13.45 1601.13 0.58 6.40 5.39 22.79 29.46 38.57 9.18

47

6347.44 6.82 7.51 1.56 6.79 5.30 5166.74 125.13 3.62 149.42 0.10 348.28 0.39 4.70 8.65 17.68 24.76 39.95 17.61

48 1.84 2102.78 1.03 10.17 0.88 2.50 4.47 2188.62 187.89 1.15 176.26 0.10 521.97 0.22 2.56 14.90 9.78 11.93 38.44 39.85

49

6278.26 6.05 3.16 1.35 5.44 0.41 4917.95 111.89 2.60 80.44 0.10 153.08 0.17 0.88 13.30 10.19 14.05 40.92 34.84

50

814.49 1.81 1.14 0.49 1.91 0.01 1090.59 96.76 0.97 23.30 0.10 78.05 0.26 2.55 14.70 0.40 1.41 48.01 50.18

51

1164.20 0.10 0.18 0.53 0.94 0.01 911.43 21.64 0.61 4.11 0.10 20.66 0.16 4.00 7.32 5.72 6.98 39.03 48.27

52

703.84 0.10 0.31 0.41 1.44 0.22 1163.39 80.08 0.39 8.62 0.10 24.49 0.10 1.30 5.92 2.05 2.10 12.54 83.30

53 7.13 10678.66 3.99 1.84 1.70 11.64 2.59 8636.41 129.25 4.88 94.84 0.10 185.64 0.22 1.68 7.70 45.46 28.20 21.14 5.19

54

11127.61 48.98 39.61 0.01 0.01 49.85 10022.32 206.44 12.05 614.78 6.41 2038.97 0.47 4.27 6.27 23.46 28.68 37.22 10.64

55

11743.42 3.99 4.43 2.08 11.21 4.46 8413.64 152.43 5.19 143.88 0.10 270.86 0.24 1.86 13.30 38.64 27.92 28.21 5.23

56

1882.09 0.12 0.59 0.52 2.42 0.01 1719.73 73.41 0.86 16.04 0.10 41.57 0.13 1.21 8.76

57

20147.68 7.05 1.65 3.61 15.78 2.12 13920.32 174.75 7.84 75.97 0.10 180.70 0.20 1.16 8.98 29.49 16.05 27.86 26.60

58

4755.68 46.54 11.66 0.01 0.01 37.02 4524.60 336.31 10.03 620.53 17.69 591.34 0.26 3.15 5.53 28.34 26.08 24.91 20.67

57

59 0.58 20884.76 23.64 3.06 8.87 17.28 8.86 17179.56 351.87 11.62 147.34 0.10 147.18 0.32 4.56 11.10 33.28 30.07 26.16 10.50

60

719.88 2.91 17.37 1.67 0.46 1.27 1536.39 190.83 1.05 230.07 0.10 478.78 0.19 4.49 4.84 13.35 13.65 10.88 62.13

61 1.22 12539.46 0.82 0.60 6.07 13.30 5.53 10795.66 100.58 9.88 71.67 0.10 64.12 0.27 0.53 7.29 18.06 15.07 28.96 37.90

62

3519.03 47.10 0.10 0.01 0.01 39.67 4214.44 195.18 9.63 478.50 25.62 296.21 0.15 2.10 2.64

63

6245.90 50.03 15.29 0.01 0.01 57.25 6180.45 238.02 10.18 727.42 21.56 1005.22 0.25 2.43 17.40 25.54 25.04 33.92 15.50

64 <LOR 49705.40 60.49 8.40 16.43 49.22 70.92 35985.05 574.17 22.59 1039.52 0.01 903.20 0.13 0.80 13.80 5.60 2.18 30.04 62.19

65

22319.89 164.92 14.80 0.01 0.01 209.43 18614.81 350.03 18.52 6190.34 35.68 8244.44 0.25 3.09 13.20 48.38 29.00 20.78 1.84

66 6.24 15007.55 20.61 18.37 5.65 21.90 61.80 13500.92 626.58 7.01 1326.97 3.29 1993.68

67 10.64 21737.82 39.51 28.34 8.57 22.19 141.38 20026.48 941.97 7.19 2374.17 6.47 3773.29

68 7.27 17283.36 28.22 30.34 6.64 25.55 89.83 14529.07 694.80 8.19 1656.48 3.78 2579.24

69 6.03 16237.88 22.64 27.29 6.03 19.28 83.39 14683.91 698.66 6.00 1450.09 4.32 2443.76

70 4.46 10033.41 37.03 37.66 5.74 18.19 79.40 12448.64 878.00 5.78 3277.71 6.63 3539.39

1 C 0.32 5595.37 4.71 17.65 1.89 7.27 17.07 5778.88 242.37 1.33 359.30 1.96 717.81

2 C 0.42 7080.00 4.43 23.09 2.83 13.23 16.83 7853.06 267.97 3.83 401.08 0.49 932.74

3 C 0.91 9564.41 9.58 36.43 4.36 13.11 14.83 10568.79 501.04 4.30 713.60 0.90 1018.77

4 C 0.53 11970.88 13.74 31.52 5.00 13.46 14.37 11815.92 434.41 5.10 602.61 1.28 1614.17

5 C 0.10 4073.91 1.09 11.56 1.62 5.31 6.04 3543.70 205.53 1.37 158.59 0.48 458.92

6 C 0.13 2880.63 51.69 5.55 2.82 11.81 87.26 4773.89 751.14 2.59 1493.00 11.25 804.38

7 C 0.13 749.42 1.58 4.09 1.35 5.16 18.28 1215.72 487.66 0.80 692.12 0.64 414.88

8 C 0.10 3727.46 7.86 14.63 2.29 6.09 5.94 3452.13 329.20 1.66 253.92 0.11 577.93

9 C 0.10 5826.47 12.80 4.71 2.59 8.94 5.91 5141.13 225.18 3.30 38.51 0.10 262.87

10 C 1.27 15813.76 23.87 37.27 6.35 16.85 23.20 12454.92 679.76 6.51 1274.29 0.90 1733.79

11 C 0.10 8699.51 7.46 20.29 3.20 11.13 11.39 6427.93 94.09 5.12 181.17 0.10 767.91

12 C 0.10 3536.30 0.73 4.30 1.57 5.33 3.29 2925.11 288.27 1.31 149.96 0.10 285.81

13 C 0.10 5063.01 5.30 17.59 2.20 6.50 7.87 4046.07 348.41 2.30 247.28 0.11 654.41

14 C 0.09 4698.10 3.19 18.82 1.75 5.96 8.85 3753.54 276.92 1.71 251.97 0.14 729.75

15 C 1.41 14514.44 26.21 28.33 9.48 14.73 22.05 11292.62 549.74 6.17 764.38 2.55 1503.80

16 C 10.32 19488.04 222.79 34.22 15.23 24.40 260.09 26208.43 1248.03 7.72 9166.18 23.47 21036.96

17 C 4.26 29463.56 82.72 55.83 13.36 47.01 86.80 31473.95 482.12 20.42 4090.29 11.31 4297.84

18 C 15.13 6712.63 104.46 39.11 7.56 52.22 490.98 8985.57 539.04 17.92 6904.21 16.57 9987.15

58

19 C 0.10 1308.63 0.10 0.09 0.61 13.56 1.23 671.19 36.58 2.67 0.10 0.10 6.14

20 C 0.10 34059.01 0.16 0.86 10.61 41.43 16.49 23581.85 335.75 18.42 7.77 1.94 47.90

21 C 0.10 6675.82 9.54 0.58 4.37 8.64 2.22 8254.96 230.93 6.08 0.55 0.10 10.51

22 C 0.10 3215.03 0.10 0.99 1.26 9.22 1.41 2542.54 214.90 2.52 15.38 0.10 52.39

* the ANZECC & ARMCANZ (2000) guidelines set an Environmental Concern Level of 2.3 µg/L for As (III) in marine waters. This figure can be adopted as a marine low reliability trigger value, to

be used only as an indicative interim working level. ^ the ANZECC & ARMCANZ (2000) guidelines give a high reliability marine guideline value for cadmium of 5.5 µg/L calculated using the

statistical distribution method with 95% protection. The 99% protection level is 0.7 µg/L, is recommended for slightly to moderately disturbed ecosystems.

Appendix table C - Metal concentrations, CNS percentages and PSA in surface sediment samples at Port Pirie. Note: CNS and PSA only undertaken on sample 1-65.

59

Appendix D – Metal concentration in core and depth horizons

Site no. Ag mg/kg

Al mg/kg As mg/kg

Cd mg/kg

Co mg/kg

Cr mg/kg

Cu mg/kg

Fe mg/kg Mn mg/kg

Ni mg/kg

Pb mg/kg Sb mg/kg

Zn mg/kg

ANZECC/ARMCANZ (2000) sediment GV-low 1

20 1.5 80 65 21 50 200

ANZECC/ARMCANZ (2000) sediment GV-high 4 70 10 370 270 52 220 410

1.0 C 0.32 5595.37 4.71 17.65 1.89 7.27 17.07 5778.88 242.37 1.33 359.30 1.96 717.81

1.1 C 0.10 1502.24 0.43 2.55 1.15 10.72 2.41 2243.95 119.09 3.13 54.05 0.37 96.06

1.2 C 0.10 3130.71 3.17 0.67 1.68 13.21 1.65 4332.93 189.99 4.11 7.14 0.43 20.47

1.3 C 0.10 4088.95 4.10 0.46 1.82 5.72 1.84 5553.11 249.66 1.27 11.76 0.24 19.93

1.4 C 0.10 4347.58 3.55 0.21 1.69 10.94 1.29 5415.95 261.32 3.30 0.10 0.16 8.54

1.5 C 1.68 4447.25 2.82 0.16 2.12 10.66 1.51 5333.71 275.58 3.45 0.10 1.00 8.21

1.6 C 0.18 4141.53 2.36 0.15 1.94 10.61 1.24 5221.15 282.46 3.31 0.10 0.10 7.40

1.7 C 0.10 4557.97 3.73 0.14 1.75 13.53 1.18 5580.22 290.91 4.10 0.10 0.62 7.74

1.8 C 0.10 4652.34 3.90 0.18 1.77 7.91 1.15 5562.85 297.02 2.16 0.10 0.24 7.65

1.9 C 0.10 5587.05 2.59 0.18 2.43 13.22 1.21 6428.30 302.82 3.93 0.10 0.06 8.51

2.0 C 0.42 7080.00 4.43 23.09 2.83 13.23 16.83 7853.06 267.97 3.83 401.08 0.49 932.74

2.1 C 0.10 2938.26 0.80 3.89 1.63 10.61 3.79 3620.78 158.17 3.19 124.87 0.72 179.64

2.2 C 2.71 4355.68 4.21 0.97 2.05 9.24 2.28 5403.98 202.41 3.10 20.20 0.54 40.69

2.3 C 0.10 5067.46 6.19 0.39 2.55 9.97 1.55 7592.87 289.77 3.57 4.21 0.21 14.90

2.4 C 0.10 5073.50 7.88 0.33 2.82 10.93 1.77 7654.58 283.08 3.98 4.29 0.60 10.83

2.5 C 0.10 5728.66 11.77 0.35 3.00 10.13 1.30 9002.41 307.05 3.92 0.10 0.76 9.69

2.6 C 0.10 6605.03 11.27 0.31 3.20 11.91 1.52 9309.05 305.46 4.23 0.10 0.10 9.67

2.7 C 0.10 5807.24 8.99 0.31 2.94 12.38 1.46 7960.11 299.62 4.50 0.10 0.10 10.65

2.8 C 1.84 5863.00 9.50 0.30 3.01 13.86 1.66 8180.09 322.75 5.10 0.10 0.54 9.29

2.9 C 0.08 6803.80 11.76 0.33 3.38 21.39 1.39 9471.91 323.10 7.44 0.10 0.22 9.61

3.0 C 0.91 9564.41 9.58 36.43 4.36 13.11 14.83 10568.79 501.04 4.30 713.60 0.90 1018.77

3.1 C 0.18 9624.67 9.97 26.53 4.21 12.73 13.44 10078.02 460.49 4.06 716.86 1.94 935.87

3.2 C 0.10 3409.96 1.85 2.07 1.79 14.14 2.47 4468.70 238.65 4.70 114.61 0.60 98.47

3.3 C 0.10 5403.91 4.01 0.84 2.50 9.85 1.67 7444.89 277.81 3.98 22.54 0.32 28.32

60

3.4 C 0.10 7088.35 3.83 0.55 2.77 9.68 1.57 7503.68 316.80 3.29 14.14 0.10 25.45

3.5 C 0.68 7087.42 3.81 0.34 2.57 9.39 1.94 7598.74 338.74 3.84 4.85 0.14 14.45

3.6 C 0.10 9535.09 4.64 0.24 2.84 11.70 1.71 8293.83 398.47 4.15 0.10 0.55 11.72

3.7 C 0.10 10113.22 5.26 0.26 3.46 11.41 1.71 9579.66 401.85 4.55 0.10 0.49 12.99

3.8 C 0.10 8540.57 5.65 0.23 3.11 10.37 1.65 8887.47 378.79 4.18 0.10 1.19 10.90

3.9 C 0.10 10561.25 7.16 0.22 3.56 12.46 1.76 9920.58 383.57 5.36 0.10 0.13 11.73

3.10 C 0.10 12710.27 8.10 0.27 3.46 13.33 2.32 11778.12 344.62 5.42 0.10 0.29 15.17

3.11 C 1.17 19720.78 7.36 0.52 5.45 18.71 3.73 17718.79 407.85 7.88 0.10 1.50 22.92

3.12 C 0.10 13701.12 6.16 0.33 4.09 14.21 2.64 13384.85 413.61 5.87 0.10 0.10 16.67

3.13 C 0.10 11258.72 8.07 0.23 3.78 12.43 2.46 10699.29 385.95 5.73 0.10 0.45 13.57

3.14 C 0.10 13079.92 6.08 0.33 3.63 13.09 2.39 11485.96 499.47 5.24 0.10 0.10 15.66

3.15 C 0.10 14168.69 4.10 0.33 3.93 14.67 2.42 13250.39 398.51 5.57 0.10 0.19 16.49

3.16 C 0.10 14810.67 4.96 0.35 3.91 15.98 3.71 13593.67 364.88 5.86 0.10 0.70 17.44

4.0 C 0.53 11970.88 13.74 31.52 5.00 13.46 14.37 11815.92 434.41 5.10 602.61 1.28 1614.17

4.1 C 2.44 13629.58 22.17 25.56 5.17 14.75 13.46 13437.00 472.19 6.04 612.08 2.13 795.13

4.2 C 0.10 6531.32 5.87 2.76 2.59 8.13 4.72 7114.16 282.09 3.07 83.61 1.60 80.13

4.3 C 0.10 5182.85 7.32 4.17 3.00 17.42 4.26 6695.60 250.67 6.47 89.20 2.68 100.39

4.4 C 0.10 4293.29 1.05 0.63 2.01 7.61 2.52 5049.11 207.90 2.95 25.98 1.16 23.04

4.5 C 0.10 4023.36 3.68 0.38 2.09 7.68 1.94 5550.71 217.67 3.78 9.33 1.09 12.86

4.6 C 0.10 4442.90 3.45 0.41 2.38 6.84 2.11 5779.53 211.94 2.98 28.46 0.93 14.27

4.7 C 0.33 4759.60 4.94 0.16 2.49 7.14 1.85 6130.31 242.13 3.40 0.10 0.17 6.81

4.8 C 0.10 4412.32 3.62 0.10 2.25 6.99 1.58 5850.44 246.84 3.25 0.10 0.63 5.98

4.9 C 0.10 4148.25 4.29 0.11 2.45 7.34 1.79 5706.27 251.85 3.49 0.70 0.15 6.88

4.10 C 0.10 4318.79 3.25 0.10 2.44 6.78 1.70 5473.62 268.16 3.51 0.10 0.25 5.89

4.11 C 0.10 5170.48 5.30 0.12 2.62 6.84 1.75 6090.24 256.87 3.54 0.10 0.34 6.14

4.12 C 0.10 4969.53 1.63 0.13 2.06 6.77 2.36 4544.75 239.02 2.51 0.10 0.27 11.78

5.0 C 0.10 4073.91 1.09 11.56 1.62 5.31 6.04 3543.70 205.53 1.37 158.59 0.48 458.92

5.1 C 0.10 3308.65 0.47 2.86 1.38 4.80 2.98 3258.82 196.15 1.21 80.49 0.67 133.32

5.2 C 0.10 2982.04 0.10 0.09 1.33 9.35 1.25 3195.28 148.62 3.34 1.25 0.10 10.98

5.3 C 0.10 3687.88 0.54 0.39 1.32 6.84 1.75 4192.32 175.70 2.88 11.22 1.05 28.30

61

5.4 C 0.10 3411.98 0.92 0.10 1.52 6.12 1.37 4393.47 184.65 2.63 0.10 0.38 4.85

5.5 C 1.55 4051.13 4.62 0.09 1.89 6.60 1.66 4491.12 227.01 3.21 0.10 0.67 9.50

5.6 C 0.10 3363.26 3.25 0.10 1.93 6.25 1.47 4367.52 200.29 3.19 0.10 0.10 4.14

5.7 C 0.10 3933.29 1.90 0.10 1.59 6.03 1.38 4693.53 189.37 2.81 0.10 0.10 4.53

5.8 C 0.10 3504.12 2.20 0.17 2.00 6.16 3.28 4489.23 190.46 2.79 2.57 0.10 16.93

5.9 C 0.10 4049.41 0.93 0.10 1.41 6.54 1.90 4274.60 201.42 2.80 0.10 0.09 5.48

5.10 C 0.10 4001.17 1.03 0.10 1.72 5.98 1.58 4028.45 192.03 2.96 0.10 0.42 5.43

5.11 C 0.10 4030.36 1.13 0.08 1.56 6.56 1.60 4058.03 202.67 2.69 0.24 0.11 9.62

6.0 C 0.13 2880.63 51.69 5.55 2.82 11.81 87.26 4773.89 751.14 2.59 1493.00 11.25 804.38

6.1 C 0.10 1741.29 79.82 1.63 4.33 11.23 38.12 4442.09 867.33 3.38 1176.59 14.46 1058.02

6.2 C 0.10 1550.15 54.35 1.87 1.79 13.07 23.24 4078.15 358.70 2.58 772.88 5.96 905.71

6.3 C 0.10 727.70 39.38 1.07 5.65 8.58 11.11 4004.58 1222.70 2.68 996.46 5.31 451.09

6.4 C 0.10 779.25 21.23 1.02 1.15 6.35 3.85 3532.44 216.23 1.22 15.45 1.01 246.50

6.5 C 0.10 606.63 19.93 0.96 0.86 8.91 1.31 3370.28 210.33 2.14 0.10 1.22 198.77

6.6 C 0.10 460.59 59.23 2.50 2.22 4.81 0.46 6734.52 177.72 0.94 0.10 7.63 264.28

6.7 C 0.10 516.39 2.47 1.03 2.45 5.04 0.99 2567.02 233.21 0.81 0.10 1.26 81.81

6.8 C 0.10 653.24 17.33 0.51 3.08 5.20 1.48 4743.00 341.09 1.51 0.10 11.08 85.49

6.9 C 0.10 12400.21 13.64 13.99 47.68 14.18 7.07 11547.39 1118.65 26.45 0.10 0.63 186.71

6.10 C 0.10 20900.98 10.84 0.43 10.58 20.39 5.66 16628.89 1576.26 9.72 0.10 0.40 30.46

6.11 C 0.10 19792.18 8.04 0.38 8.94 19.40 6.00 15526.84 1860.95 9.55 0.10 0.27 28.11

6.12 C 0.10 20211.86 2.65 0.35 8.01 19.57 5.86 15287.22 1892.63 8.95 0.10 0.10 27.40

6.13 C 3.27 16863.15 1.48 0.40 7.84 17.36 5.77 13908.67 1939.11 8.15 0.10 0.17 24.46

6.14 C 0.74 23342.90 3.10 0.54 9.84 23.97 6.36 18358.81 1750.14 10.84 0.10 0.10 32.09

6.15 C 0.10 24925.91 3.86 0.75 11.73 26.48 7.24 20345.88 1511.69 12.71 0.10 0.32 37.90

7.0 C 0.13 749.42 1.58 4.09 1.35 5.16 18.28 1215.72 487.66 0.80 692.12 0.64 414.88

7.1 C 0.09 808.44 2.27 4.23 1.65 6.89 18.76 1277.36 513.38 1.75 697.62 0.07 434.68

7.2 C 0.13 891.04 2.03 5.00 1.53 8.45 19.16 1335.79 502.61 2.05 698.82 0.36 462.24

7.3 C 3.11 915.99 2.95 8.65 1.53 8.46 18.61 1320.07 479.50 2.16 721.25 2.57 565.46

7.4 C 2.37 757.14 1.44 24.62 1.69 14.89 13.57 1019.15 354.85 4.57 603.43 2.29 923.48

7.5 C 1.49 1064.29 5.11 36.58 2.64 14.63 17.18 1423.45 578.20 4.24 802.51 2.27 1600.47

62

7.6 C 0.30 562.36 0.10 23.14 1.36 8.09 9.13 601.33 267.25 2.25 521.12 0.34 875.78

7.7 C 0.11 598.92 2.37 16.29 1.62 10.08 7.38 732.64 237.67 3.07 590.05 3.22 1000.46

7.8 C 0.10 1096.37 7.39 13.77 1.89 17.39 2.28 1370.66 271.05 5.56 406.68 1.88 791.18

7.9 C 0.10 1206.80 0.10 0.12 1.59 20.39 1.29 1751.13 96.19 7.76 0.10 0.10 1.97

7.10 C 0.10 1226.45 0.21 0.15 1.81 22.28 0.84 1802.47 109.19 8.40 0.18 0.10 4.40

7.11 C 0.10 1889.84 1.26 0.18 1.61 21.21 1.04 2442.70 137.40 7.72 0.85 0.10 3.20

7.12 C 0.10 2171.36 0.16 0.15 1.84 12.03 1.18 2428.81 138.31 4.15 0.30 0.10 4.20

7.13 C 0.10 3242.79 0.22 0.23 1.75 8.68 1.11 3270.68 123.24 3.36 0.99 0.10 5.16

7.14 C 0.10 4800.59 0.10 1.22 2.07 11.21 3.85 4386.03 325.64 3.56 86.81 0.10 89.82

8.0 C 0.10 3727.46 7.86 14.63 2.29 6.09 5.94 3452.13 329.20 1.66 253.92 0.11 577.93

8.1 C 1.61 3862.62 0.15 2.35 1.51 7.06 2.90 3092.38 246.07 1.73 79.25 0.36 151.36

8.2 C 0.54 3070.93 0.10 0.92 1.36 7.56 2.00 2972.46 212.14 3.19 27.59 0.10 64.86

8.3 C 0.10 3330.10 0.10 0.12 1.55 6.07 1.50 3216.19 208.32 2.38 6.53 0.14 21.16

8.4 C 0.10 3602.80 0.15 0.09 1.68 5.92 1.29 3695.03 221.78 2.93 2.23 0.10 16.41

8.5 C 0.10 3166.72 0.60 0.10 1.72 5.38 1.08 3595.86 222.71 2.64 0.10 0.10 4.72

8.6 C 0.10 3274.31 0.61 0.10 1.73 5.18 1.09 3726.79 224.14 3.03 0.10 0.10 3.95

8.7 C 1.86 4118.58 0.31 0.09 2.04 6.03 1.61 3725.30 237.13 2.97 0.10 0.20 6.19

8.8 C 1.11 3824.84 1.60 0.10 1.86 5.83 1.38 4075.34 234.61 3.15 0.10 0.10 4.97

8.9 C 0.17 3738.82 1.59 0.10 2.32 5.73 1.69 3974.31 247.34 3.60 0.10 0.10 5.01

8.10 C 0.10 3527.11 2.26 0.10 2.20 5.43 1.25 4071.99 254.10 2.93 0.10 0.10 4.08

8.11 C 0.10 3899.57 2.08 0.10 2.57 5.75 1.72 4126.76 251.66 3.53 0.10 0.10 5.51

8.12 C 0.10 3581.12 2.33 0.10 2.02 5.45 1.23 3917.45 259.24 2.86 0.10 0.10 5.17

9.0 C 0.10 5826.47 12.80 4.71 2.59 8.94 5.91 5141.13 225.18 3.30 38.51 0.10 262.87

9.1 C 2.81 4833.44 7.51 4.90 2.31 7.64 5.32 4728.96 222.49 2.94 40.21 0.10 273.23

9.2 C 0.42 3802.05 1.92 4.18 1.50 6.80 3.58 3605.85 280.85 1.80 29.75 0.10 235.26

9.3 C 0.10 2054.27 0.25 1.77 1.45 4.74 1.54 2049.05 289.76 0.96 12.44 0.10 118.88

9.4 C 0.10 1677.66 0.40 0.97 0.86 4.31 1.10 1841.91 293.55 0.77 7.14 0.10 80.14

9.5 C 0.10 1556.78 0.10 0.33 1.23 5.58 0.77 2031.72 276.09 1.77 0.26 0.10 32.38

9.6 C 0.10 1653.70 0.10 0.08 1.10 7.74 0.51 2195.76 252.22 2.48 0.10 0.10 15.43

9.7 C 0.92 2520.49 5.31 0.28 2.08 6.24 1.01 3760.16 271.10 2.67 0.10 0.10 23.60

63

9.8 C 0.73 3060.65 5.62 0.10 2.21 5.61 0.93 4444.47 280.62 2.84 0.10 0.10 6.82

9.9 C 0.10 3196.45 4.78 0.09 2.01 5.42 0.98 4200.18 294.61 2.95 0.10 0.13 9.55

9.10 C 0.10 3454.46 5.07 0.10 2.60 5.52 1.02 4415.36 302.61 3.43 0.10 0.10 5.02

9.11 C 0.10 3984.65 4.88 0.10 2.39 5.90 1.30 4626.19 312.35 3.33 0.10 0.10 6.76

10.0 C 1.27 15813.76 23.87 37.27 6.35 16.85 23.20 12454.92 679.76 6.51 1274.29 0.90 1733.79

10.1 C 3.39 13533.86 15.54 53.90 5.66 17.03 23.31 11237.25 653.42 6.24 1004.36 0.70 1539.55

10.2 C 1.32 10937.08 10.17 15.41 4.10 13.54 13.34 7842.23 431.77 4.92 779.90 0.58 737.12

10.3 C 0.10 3804.53 0.64 2.65 1.89 7.64 3.76 3201.54 247.53 2.04 217.80 0.10 175.20

10.4 C 0.10 2709.34 0.10 1.02 1.57 9.54 2.16 2544.90 185.60 2.86 112.32 0.28 77.92

10.5 C 1.11 2929.05 0.10 0.16 1.32 9.62 1.01 3059.80 183.76 3.39 11.72 0.10 17.49

10.6 C 0.38 4444.08 0.75 0.10 1.93 6.66 1.04 4394.25 265.72 2.40 0.10 0.10 9.20

10.7 C 0.10 4633.51 0.66 0.10 1.86 7.13 1.04 4576.90 263.23 2.45 0.10 0.10 5.91

10.8 C 0.10 5198.04 0.39 0.12 1.84 6.89 1.26 4532.71 269.98 2.12 0.10 0.10 6.66

10.9 C 0.10 4580.65 0.33 0.10 2.15 6.50 1.35 4179.24 276.73 2.62 0.10 0.16 5.66

10.10 C 0.10 5305.57 0.20 0.10 1.73 7.13 1.13 4643.79 279.15 2.74 0.10 0.10 5.97

10.11 C 0.10 5231.45 0.39 0.10 1.63 7.01 1.13 4549.60 282.87 2.76 0.10 0.10 5.80

10.12 C 0.10 6100.89 1.00 0.12 2.27 7.74 1.22 5064.19 287.97 3.07 0.78 0.10 16.81

11.0 C 0.10 8699.51 7.46 20.29 3.20 11.13 11.39 6427.93 94.09 5.12 181.17 0.10 767.91

11.1 C 0.10 6501.92 11.24 26.28 3.32 10.48 11.57 6049.17 96.27 5.16 218.47 0.10 1015.01

11.2 C 0.10 6432.26 11.64 26.74 3.07 9.87 11.20 5626.34 88.61 4.78 212.84 0.10 998.80

11.3 C 0.10 7860.18 12.52 26.35 3.11 10.99 10.27 6542.89 99.04 5.17 208.17 0.10 963.74

11.4 C 0.10 5094.61 8.06 16.15 2.50 9.52 6.26 4769.27 97.31 4.10 135.65 0.10 652.54

11.5 C 0.10 1616.76 0.08 2.96 1.26 10.19 1.72 1658.82 85.34 3.39 32.65 0.10 168.30

11.6 C 0.10 2817.58 0.21 2.01 1.47 8.69 1.63 2560.63 80.80 3.38 19.50 0.10 84.67

11.7 C 0.10 2867.11 0.79 0.66 1.88 9.02 1.34 2666.42 81.40 3.78 7.04 0.10 25.60

11.8 C 0.10 3274.98 0.74 0.25 1.91 6.58 1.57 3172.79 88.31 2.97 0.74 0.10 8.46

11.9 C 0.10 2646.51 0.54 0.22 1.67 5.79 1.08 2810.09 81.20 2.79 0.57 0.10 4.52

11.10 C 0.10 2473.13 0.45 0.19 1.83 7.81 1.27 2719.15 87.54 3.78 0.50 0.10 4.78

11.11 C 0.10 2934.23 5.49 0.23 2.02 5.73 1.60 3369.92 92.26 3.49 0.09 0.10 5.79

11.12 C 0.10 2720.56 1.29 0.23 2.06 5.27 1.15 3018.78 90.25 2.77 0.28 0.10 5.61

64

11.13 C 0.10 2786.78 5.61 0.32 2.35 6.67 1.53 3463.17 92.49 3.98 1.84 0.10 6.98

11.14 C 0.10 2830.84 5.18 0.49 2.26 4.37 1.47 3254.60 93.61 3.33 3.75 0.10 14.40

11.15 C 0.66 2852.80 6.72 0.24 2.16 5.27 1.32 3245.13 86.23 3.36 0.54 0.10 4.07

11.16 C 0.10 2777.50 3.52 0.27 2.13 6.03 1.62 3122.51 94.51 3.22 0.44 0.10 6.54

12.0 C 0.10 3536.30 0.73 4.30 1.57 5.33 3.29 2925.11 288.27 1.31 149.96 0.10 285.81

12.1 C 0.10 2851.89 0.39 1.47 1.45 4.93 1.44 2611.70 230.34 1.89 56.83 0.71 114.07

12.2 C 0.10 2173.30 0.36 0.51 2.00 4.87 2.04 2176.06 89.60 2.41 14.13 0.10 27.29

12.3 C 0.10 2235.21 1.93 0.23 2.09 4.13 1.23 2447.73 89.00 2.50 4.57 0.10 9.46

12.4 C 0.10 2632.84 9.11 0.34 2.37 4.49 0.90 3614.39 89.45 3.34 1.74 0.10 8.57

12.5 C 0.10 4023.62 12.13 0.34 2.80 5.76 1.33 4379.33 105.99 4.44 0.50 0.10 5.35

12.6 C 0.10 2914.52 3.08 0.16 1.86 4.97 1.23 2950.21 98.30 2.98 0.31 0.10 4.44

12.7 C 0.10 3168.37 3.82 0.23 2.24 4.88 1.10 2919.09 100.00 2.90 0.73 0.10 6.73

12.8 C 0.10 3311.08 2.54 0.52 2.02 4.86 2.39 3265.47 105.41 2.48 16.38 0.10 19.78

12.9 C 0.10 3197.32 3.64 0.17 1.84 4.64 1.38 2811.61 98.63 3.03 0.90 0.10 6.04

12.10 C 0.10 4402.13 6.83 0.10 2.18 5.71 1.45 4020.31 296.76 3.31 0.10 0.05 4.81

12.11 C 0.10 4153.04 6.48 0.10 1.79 5.65 1.24 3694.66 283.52 3.69 0.10 0.05 4.64

12.12 C 0.10 4341.25 2.08 0.10 2.02 5.69 1.15 3381.29 282.16 2.88 0.10 0.36 4.76

12.13 C 0.10 3642.97 3.40 0.10 1.87 7.04 0.87 3166.20 275.44 3.56 0.10 0.18 3.56

12.14 C 0.10 3881.59 5.98 0.10 2.09 5.46 1.11 3723.07 286.22 3.32 0.10 0.10 4.02

12.15 C 0.10 3610.09 4.28 0.10 2.14 5.13 1.06 3466.71 296.71 3.04 0.10 0.11 4.01

13.0 C 0.10 5063.01 5.30 17.59 2.20 6.50 7.87 4046.07 348.41 2.30 247.28 0.11 654.41

13.1 C 0.10 4701.18 1.89 3.37 2.13 7.77 4.62 3647.87 290.87 2.89 160.94 0.52 191.43

13.2 C 0.10 3374.54 0.99 0.54 1.80 6.12 1.97 3315.33 252.49 3.13 37.35 0.34 40.12

13.3 C 0.10 3896.53 6.86 0.10 1.80 5.55 1.98 3568.52 268.10 3.62 0.10 0.29 6.75

13.4 C 0.10 3244.04 1.19 0.10 1.85 4.76 1.20 3157.73 259.09 2.90 0.28 0.10 7.67

13.5 C 0.10 3045.08 1.85 0.10 1.75 5.00 1.13 2969.41 256.89 2.85 0.21 0.18 5.34

13.6 C 0.10 3089.04 1.99 0.10 1.70 4.51 0.78 3150.08 259.11 2.87 0.10 0.10 3.58

13.7 C 0.10 3086.83 1.17 0.10 1.40 4.20 1.33 2777.53 258.70 2.47 1.00 0.10 11.95

13.8 C 0.10 2597.83 1.60 0.10 1.57 3.95 0.99 2643.45 270.58 2.76 0.10 0.10 3.22

13.9 C 0.10 3015.88 1.75 0.10 1.89 4.66 1.15 2840.41 259.93 2.66 0.10 0.10 4.59

65

13.10 C 0.10 3144.16 3.40 0.10 1.78 4.54 1.03 3319.78 264.95 3.07 0.10 0.11 3.91

13.11 C 0.10 2946.08 6.86 0.10 2.18 4.55 1.22 3678.56 261.40 3.87 0.10 0.10 3.49

13.12 C 0.10 2989.88 3.35 0.10 1.53 4.64 1.06 2956.43 267.58 3.01 0.10 0.10 3.06

13.13 C 0.10 2865.52 2.18 0.10 1.43 4.79 0.94 2665.29 266.22 2.65 0.10 0.10 2.92

13.14 C 0.10 2969.77 1.17 0.10 1.80 4.47 1.28 2872.56 278.25 3.18 0.10 0.10 4.00

13.15 C 0.10 2838.32 6.26 0.10 2.12 4.44 0.98 3545.30 273.96 3.18 0.10 0.26 6.02

13.16 C 0.10 3397.15 5.47 0.10 1.90 5.09 1.14 3400.37 267.82 3.23 0.10 0.10 4.09

13.17 C 0.10 12169.73 6.94 0.10 3.85 12.98 1.98 9173.20 493.69 5.42 0.10 0.10 13.23

14.0 C 0.09 4698.10 3.19 18.82 1.75 5.96 8.85 3753.54 276.92 1.71 251.97 0.14 729.75

14.1 C 0.10 4119.37 1.40 4.51 1.69 5.06 5.56 3283.98 256.55 1.81 133.68 0.35 189.98

14.2 C 0.10 4388.73 1.30 0.15 1.48 6.14 1.53 3565.94 221.62 2.80 1.50 0.10 22.71

14.3 C 0.10 4516.38 2.34 0.10 1.73 6.29 1.55 3934.89 230.73 2.98 7.55 0.22 13.64

14.4 C 0.10 4513.16 3.38 0.12 2.01 6.23 2.79 4348.73 243.93 2.58 0.10 0.15 6.71

14.5 C 0.10 4611.44 0.69 0.11 1.48 6.00 1.77 3718.48 234.92 1.64 0.10 0.10 6.78

14.6 C 0.10 4804.70 2.56 0.26 1.91 6.25 2.00 4091.54 247.54 1.66 4.06 0.41 8.70

14.7 C 0.10 5049.42 0.60 0.22 1.55 6.26 1.56 4039.74 251.25 1.38 0.10 0.10 7.84

14.8 C 0.10 4598.56 0.46 0.11 1.74 5.65 1.33 3553.30 256.11 0.63 0.10 0.10 5.74

14.9 C 0.10 4814.49 0.76 0.15 1.84 5.73 1.32 4054.87 256.09 1.45 0.10 0.26 5.32

14.10 C 0.10 4771.06 1.42 0.16 1.49 6.07 1.67 4006.77 255.11 1.41 0.10 0.10 5.72

15.0 C 1.41 14514.44 26.21 28.33 9.48 14.73 22.05 11292.62 549.74 6.17 764.38 2.55 1503.80

15.1 C 2.23 17784.05 47.46 43.68 10.06 17.69 23.90 13131.23 747.08 7.20 1182.06 0.87 2367.48

15.2 C 1.47 13863.29 31.08 31.87 6.43 13.00 16.61 10506.15 610.23 4.31 878.65 3.54 1207.39

15.3 C 0.10 10253.63 10.87 5.26 3.93 9.63 7.95 7656.67 470.10 3.16 239.42 3.05 207.80

15.4 C 0.10 6953.68 6.10 1.60 3.02 7.40 4.87 5729.25 377.78 2.33 74.36 1.89 65.81

15.5 C 0.10 7066.97 3.83 0.69 1.92 7.87 2.38 5312.35 334.07 2.66 12.05 0.24 25.59

15.6 C 0.10 6140.30 4.28 0.39 2.23 7.00 2.52 4924.19 322.23 2.67 6.15 0.10 15.04

15.7 C 0.10 6170.00 4.40 0.45 2.26 8.13 2.55 4664.11 324.97 2.84 9.38 0.10 14.08

15.8 C 0.10 6286.27 3.21 0.28 2.16 7.21 2.11 4887.04 317.22 2.27 0.10 0.10 9.75

15.9 C 0.10 6859.78 3.25 0.27 2.22 7.65 1.91 5184.04 320.98 2.19 0.10 0.32 9.22

15.10 C 0.10 6950.77 2.33 0.27 2.24 7.91 2.00 5197.07 329.72 2.28 0.10 0.10 8.97

66

16.0 C 10.32 19488.04 222.79 34.22 15.23 24.40 260.09 26208.43 1248.03 7.72 9166.18 23.47 21036.96

16.1 C 0.12 26214.58 8.97 2.73 7.63 23.24 28.94 20263.59 663.18 8.73 878.52 0.84 1254.35

16.2 C 0.10 27578.27 0.10 1.17 7.11 23.47 11.23 19513.87 576.52 8.98 55.26 0.26 151.17

16.3 C 0.10 40989.80 0.10 1.71 12.89 32.95 19.55 32633.50 491.48 16.32 135.36 1.42 249.85

16.4 C 0.10 21848.25 0.10 0.82 6.67 20.66 10.20 16235.12 343.80 7.96 64.95 0.10 75.58

16.5 C 0.10 26260.60 0.10 0.87 7.03 22.73 9.89 18775.36 311.05 8.83 52.15 0.42 56.96

16.6 C 0.10 20519.27 0.10 0.74 5.39 22.36 8.61 14017.02 203.47 7.73 31.96 0.54 36.71

16.7 C 0.10 23765.09 0.10 0.80 6.21 22.96 8.50 17015.29 252.59 8.60 4.65 0.64 29.32

16.8 C 0.10 14351.60 0.10 0.55 4.41 22.23 5.71 10192.19 161.68 7.26 16.66 0.18 20.47

16.9 C 0.10 9777.78 0.10 0.51 2.98 26.61 4.42 7141.30 99.10 7.73 12.53 0.12 15.47

17.0 C 4.26 29463.56 82.72 55.83 13.36 47.01 86.80 31473.95 482.12 20.42 4090.29 11.31 4297.84

17.1 C 0.10 38227.43 5.76 3.93 9.08 34.00 20.89 23590.36 209.32 11.85 622.54 1.50 437.20

17.2 C 0.10 45224.89 0.10 1.24 7.79 40.82 21.28 29922.74 209.52 13.69 14.18 2.04 69.50

17.3 C 0.10 56351.67 0.10 1.33 10.35 47.07 31.99 37507.95 248.03 19.02 0.46 2.98 65.80

17.4 C 0.10 56257.21 0.10 1.14 10.31 45.94 23.15 34358.27 241.33 18.51 0.46 2.45 65.52

17.5 C 0.10 58786.24 0.10 0.84 10.24 47.40 21.25 31135.54 249.13 17.90 4.55 2.82 77.60

18.0 C 15.13 6712.63 104.46 39.11 7.56 52.22 490.98 8985.57 539.04 17.92 6904.21 16.57 9987.15

18.1 C 9.01 3556.19 13.44 5.76 1.94 19.14 64.58 2828.96 272.89 4.81 2347.53 6.58 1548.44

18.2 C 14.58 10021.44 144.37 49.54 7.31 21.70 131.12 10888.32 458.33 7.08 5125.24 25.58 9696.85

18.3 C 16.46 16510.40 150.79 93.11 10.78 26.49 328.92 17401.57 925.12 9.26 10588.09 34.35 13725.30

18.4 C 13.40 13643.87 35.07 10.99 5.03 25.10 92.90 12203.83 736.58 8.04 7761.19 7.54 5107.27

18.5 C 9.47 6196.74 26.64 24.98 2.70 14.15 40.71 6184.65 284.71 3.29 2805.63 4.91 1632.58

18.6 C 0.10 4403.01 0.25 1.02 0.87 9.64 2.67 3653.54 206.97 1.06 105.91 0.10 169.22

18.7 C 0.10 2561.54 0.10 0.67 0.48 8.82 1.47 1408.46 123.64 1.07 46.68 0.10 103.05

18.8 C 0.10 2471.03 0.10 0.31 1.41 11.70 0.98 1792.86 176.89 2.25 8.56 0.10 48.18

18.9 C 0.10 4939.79 5.41 0.46 4.35 7.34 1.41 5144.91 391.05 2.16 16.53 0.10 35.35

18.10 C 0.10 9140.11 12.40 0.77 15.07 10.65 3.65 8914.44 672.44 6.44 65.63 0.10 75.89

19.0 C 0.10 1308.63 0.10 0.09 0.61 13.56 1.23 671.19 36.58 2.67 0.10 0.10 6.14

19.1 C 0.10 1172.42 0.10 0.10 0.35 5.05 3.47 645.90 42.38 0.14 0.45 0.10 8.87

19.2 C 0.10 1439.36 0.10 0.10 0.62 16.44 5.00 941.53 41.17 3.96 7.53 0.10 12.03

67

19.3 C 0.10 1180.17 0.10 0.07 0.69 10.61 2.34 802.91 31.34 2.24 6.61 0.10 10.67

19.4 C 0.10 1176.38 0.10 0.10 0.26 12.24 1.06 762.33 30.93 2.53 0.10 0.10 2.28

19.5 C 0.10 1746.18 0.10 0.10 0.93 50.46 1.02 1460.52 53.67 17.55 0.10 0.35 1.21

19.6 C 0.10 2158.84 0.10 0.13 0.79 6.65 0.74 1805.96 53.63 1.28 0.10 0.10 2.23

19.7 C 0.10 1642.79 0.10 0.13 0.64 7.85 0.42 1366.48 49.55 1.32 0.10 0.10 2.04

19.8 C 0.10 2032.91 0.10 0.09 0.55 6.91 0.57 1806.11 57.69 1.29 0.10 0.10 3.04

19.9 C 0.10 1583.43 0.10 0.08 0.76 6.75 0.37 1364.11 47.85 1.81 0.10 0.10 1.48

19.10 C 0.10 1478.19 0.10 0.10 1.07 10.65 0.44 1306.51 46.91 3.21 0.10 0.10 1.24

19.11 C 0.10 3573.29 7.36 0.17 1.63 7.09 1.33 3875.86 90.14 3.68 0.10 0.40 3.80

19.12 C 0.10 4735.26 8.93 0.16 1.79 7.40 1.82 4248.32 113.53 3.62 0.10 1.08 4.86

19.13 C 0.10 4854.61 4.64 0.15 1.95 7.20 1.63 3701.50 112.86 2.47 0.10 0.10 5.71

20.0 C 0.10 34059.01 0.16 0.86 10.61 41.43 16.49 23581.85 335.75 18.42 7.77 1.94 47.90

20.1 C 0.10 19503.74 0.09 0.67 5.78 35.51 8.74 15347.81 220.08 13.55 5.14 0.69 24.44

20.2 C 0.10 12677.38 1.94 0.48 9.48 31.04 9.66 9606.39 130.87 14.57 0.20 0.30 16.64

20.3 C 0.10 16645.40 0.10 0.44 6.80 45.43 9.37 10527.27 120.93 17.94 0.10 0.48 20.20

20.4 C 0.10 12039.91 0.10 0.59 10.37 35.20 25.72 8639.50 47.61 19.00 6.17 0.10 20.95

20.5 C 0.10 38470.93 0.10 1.32 16.31 39.79 33.15 25838.06 105.82 24.01 2.74 0.33 55.58

20.6 C 0.10 31692.66 0.10 1.52 9.61 34.87 18.72 24873.12 94.91 16.35 4.22 0.20 47.79

21.0 C 0.10 6675.82 9.54 0.58 4.37 8.64 2.22 8254.96 230.93 6.08 0.55 0.10 10.51

21.1 C 0.10 11742.56 11.33 0.70 5.96 12.10 3.04 10811.50 293.73 7.59 0.76 0.10 14.11

21.2 C 0.10 8258.60 6.96 0.62 5.12 9.27 3.08 8652.57 277.36 6.16 1.46 0.10 13.01

21.3 C 0.10 7788.96 9.13 0.59 4.94 9.12 2.70 8242.33 256.36 6.10 0.78 0.10 11.86

21.4 C 0.10 8294.95 12.30 0.70 5.80 10.63 2.43 9883.81 336.47 7.24 0.83 0.10 13.53

21.5 C 0.10 8282.17 12.86 0.78 6.12 11.82 2.45 10169.96 351.65 7.48 1.49 0.10 14.05

21.6 C 0.10 9670.20 13.97 0.87 6.52 13.38 2.01 11240.30 300.90 8.19 2.42 0.10 15.16

21.7 C 0.10 652.03 0.10 0.46 0.98 20.69 0.65 552.31 36.33 6.93 12.01 0.10 30.20

21.8 C 0.10 15957.08 11.24 1.09 13.74 34.35 6.47 21192.89 554.84 17.80 0.52 0.60 31.91

21.9 C 0.10 17258.90 10.96 1.18 15.08 48.48 7.99 22760.55 497.58 23.56 0.69 1.57 35.29

21.10 C 0.10 18190.40 3.46 0.97 13.37 34.36 9.69 19737.31 476.81 17.87 1.22 1.08 38.87

21.11 C 0.10 17554.54 0.19 0.81 9.98 28.06 10.16 16609.38 391.19 14.64 1.10 1.30 37.88

68

21.12 C 0.10 16726.53 0.61 0.81 12.33 27.49 11.19 16254.04 232.69 15.04 1.64 0.65 37.87

21.13 C 0.10 15386.41 2.17 0.90 19.71 31.11 10.98 16553.87 175.08 18.36 3.60 0.71 37.83

22.0 C 0.10 3215.03 0.10 0.99 1.26 9.22 1.41 2542.54 214.90 2.52 15.38 0.10 52.39

22.1 C 0.10 1970.50 0.10 0.73 0.56 12.99 0.80 1484.16 172.09 3.24 10.37 0.10 43.71

22.2 C 0.10 3562.06 0.25 0.17 1.13 13.24 0.78 3096.30 202.33 3.64 0.10 0.22 4.73

22.3 C 0.10 3456.74 0.11 0.16 1.56 12.72 2.13 2814.55 203.48 3.39 0.10 0.10 5.84

22.4 C 0.10 2792.00 0.10 0.08 1.31 10.43 0.66 2430.76 167.98 3.46 0.10 0.10 2.79

22.5 C 0.10 3559.00 2.50 0.19 1.93 7.67 1.01 3411.40 219.89 2.96 0.10 0.10 4.41

22.6 C 0.10 3417.76 2.27 0.15 2.00 10.16 1.14 3301.18 254.99 3.80 0.10 0.08 6.54

22.7 C 0.10 3421.38 1.00 0.17 1.54 10.11 1.09 2941.65 241.91 2.91 0.10 0.10 4.32

22.8 C 0.10 908.13 0.10 0.53 0.47 26.83 0.80 689.58 98.41 7.70 23.08 0.10 35.59

Appendix Table D - Metal concentrations within core sediment samples (core 1.0 – 22.0C) at Port Pirie.