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Monitoring Heavy Metals in Goulburn-Murray Waterways

using Passive Sampling with Artificial Mussels (AM) – Pilot

Study (Trial of AM Technology)

February 2010

2

Cover layout and photos: Golam Kibria

General disclaimer

This publication may be of assistance to you however, the Goulburn Murray Rural Water Corporation, the City University of Hong Kong, the

University of Hong Kong and the Department of Primary Industries and any of its employees do not guarantee that the publication is without flaw

of any kind or is wholly appropriate for your particular purposes, and therefore disclaims all liability for any error, loss or other consequences which

may arise from you relying on any information contained within this publication

The technical report was the outcome of an international research collaboration between the Goulburn Murray Rural Water Corporation, Tatura,

Victoria, Australia (G-MW), the Centre for Marine Environmental Research and Innovative Technology, City University of Hong Kong (CityU), the

University of Hong Kong (HKU) and the Department of Primary Industries, Future Farming System Research Division, Werribee Centre,

Melbourne, Australia (DPI)

: G-MW, CityU, HKU and DPI

G-MW Docs: 2806033

ISBN: 978-1-876356-19-4

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Monitoring Heavy Metals in Goulburn-Murray Waterways Using

Passive Sampling with Artificial Mussels (AM) – Pilot Study

(trial of AM technology)

By

Dr Golam Kibria

Goulburn Murray Rural Water Corporation

Tatura, Australia

Gavin Rose

Department of Primary Industries, Future Farming Systems Research Division

Werribee Centre, Melbourne, Australia

Chair Professor T.C. Lau, Dr Christie Y. K. Lung, Dr Alice KY Chan

Department of Biology and Chemistry, City University of Hong Kong

Chair Professor Rudolf Wu

School of Biological Sciences,

The University of Hong Kong, Hong Kong

February 2010

4

Citation

Kibria, G., Rose, G., Lau, T.C., Lung, Y.K., Chan, A.K.Y., Wu, R. (2010). Monitoring heavy Metals in Goulburn-Murray

waterways using passive sampling with artificial mussels (AM) – Pilot Study (trial of AM technology). Report prepared

under a research collaboration agreement between Goulburn Murray Rural Water Corporation, Tatura, Australia, the

City University of Hong Kong, the University of Hong Kong, and the Department of Primary Industries, Werribee,

Victoria, Australia. 29p.

Correspondence about the technical report and R&D

Dr Golam Kibria

Goulburn Murray Rural Water Corporation

40 Casey Street, Tatura, VIC 3616

Australia

[email protected]

Web site: http://www.g-mwater.com.au/projects/researchanddevelopment

Acknowledgements

G-MW: EMPA12 Reference Team Members, David Fehring (CGIA), Ross Stanton (TIA), Rob William

(MVIA)

DPI: Dr Adam Wightwick

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1. Executive summary

This pilot project verified novel artificial mussel (AM) technology for monitoring heavy metals in waterways

for the first time in Australia. The ability to deploy and retrieve AMs in selected risk areas and analyse and

interpret AM results was confirmed for five sites within Goulburn-Murray Water Irrigation Areas. The work

is part of ‘global artificial mussels watch program’ being run in eight countries including Australia.

The ‘Artificial mussel (AM)’ passive sampling is a device that collects or accumulates pollutants (heavy

metals or HM) independently through a diffusion barrier onto a sorbent medium. The AM device consists of

a polymer ligand suspended in artificial seawater/freshwater within Perspex tubing and enclosed with semi-

permeable gel at both ends.

The AMs were deployed in irrigation channels and rivers within G-MW catchments during the 2007-08

irrigation seasons (sites were Kerang, Burramine, Shepparton, Mooroopna, and Nagambie) as part of pilot

trial of AM technology. AM deployed in waterways had accumulated both targeted and non-targeted

metals. The targeted metals are cadmium, copper, mercury, and zinc. In addition, AM also accumulated

some non-targeted metals such as chromium, cobalt, iron, and nickel. The AM results showed both spatial

and temporal variations between and within the monitoring sites.

The order of accumulation of metals in AM was as follows:

• Targeted metals : Zn>Cu>Cd>Hg

• Non-targeted metals : Fe>Ni>Co>Cr

The pilot study conducted found that AM is a reliable tool for monitoring heavy metals in waterways and

could be useful in risk assessment for various water utilities including recycled water, treated wastewaters,

rivers, and irrigation channels etc.

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2. Contents

1. Executive summary …………………………………………………………………………………………… 5

2. Contents …………………………………………………………………………………………… 6

3. Acronyms and glossary …………………………………………………………………………………. 7

4. Background …………………………………………………………………………………. 8

5. Scope of the work …………………………………………………………………………………. 9

6. Objectives …………………………………………………………………………………………… 9

7. Study description …………………………………………………………………………………………… 9

7.1: Heavy metals monitoring strategy ……………………………………………………………….. 9

7.2 . Monitoring sites………………………………………………………………………………………………. 11

7.3. Monitoring schedule…………………………………………………………………………………………. 11

7.3.1 : Sampling frequency………………………………………………………………………… 11

8. Methods ………………………………………………………………………………………………………… 14

8.1 : Deployment and retrieval of artificial mussels (AM)……………………………………………......... 14

8.2 : Storage of AM before deployment……………………………………………………………………… 15

8.3 : Shipment of AM to Hong Kong………………………………………………………………………… 15

9. Water quality ……………………………………………………………………………………………………. 15

9.1 : Water temperature……………………………………………………………………………………. 15

9.2 : Water hardness………………………………………………………………………………………… 16

10. Analytical techniques…………………………………………………………………………………………. 17

11. Quality assurance………………………………………………………………………………………………. 17

12. Occupational health and safety………………………………………………………………………………. 17

13. Results …………………………………………………………………………………………………………… 18

14. Discussion……………………………………………………………………………………………………… 18

15. Conclusion……………………………………………………………………………………………………… 19

16. References……………………………………………………………………………………………………… 27

17. Appendix

Abstract of paper presented - Australasian Society for Ecotoxioclogy, 2009……………………………………….. 28

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3. Acronyms and glossary

Artificial mussel : see passive sampling

CityU : City University of Hong Kong

Chelation: A metallic ion bonds at two or more coordination points to a ligand to form a complex molecule.

This creates a ring structure and greatly reduces the chemical reactivity of the metallic ion but greatly

increases its solubility and availability.

DPI : Department of Primary Industries

G-MW : Goulburn Murray Rural Water Corporation

Guideline trigger values : These are the concentrations (or loads) of the key performance indicators

measured for the ecosystem, below which there exists a low risk that adverse biological (ecological) effects

will occur. They indicate a risk of impact if exceeded and should ‘trigger’ some action, either further

ecosystems specific investigations or implementation of management /remedial actions

Heavy metals : are a group of metallic elements with an atomic weight greater than 20 and characterized by

similar electron distribution in their external shell.

Ligand : An ion, a molecule, or a molecular group that binds to another chemical entity to form a larger

complex

Milli-Q : also called high purity water, refers to water that has been purified and deionized to a high

degree by water purification systems.

Passive sampling : A device that collects or accumulates pollutants (eg. Heavy metals) independently

through a diffusion barrier onto a sorbent medium without use of a vacuum source or energy

Polymer: The resulting form of many small molecules joined together, a mixture of compounds by a specific

molecular process called polymerization

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4. Background

Heavy metals can pollute water supply systems through natural deposits, waste discharged from

mining, industrial and agricultural activities. Water contaminated with heavy metals may be

unsuitable for irrigation, human drinking water, livestock drinking, aquatic ecosystems protection

and recreation and aquaculture. Metal pollution may reduce biodiversity, eliminate sensitive

species or reduce species abundance through reproductive impairment and increase diseases.

Aquatic flora and fauna such as invertebrates (molluscs) and fish can bioaccumulate heavy metal

levels up to a thousand times higher than the ambient environment, thereby posing health risks to

human and top predators through food consumption. Irrigation water may transport dissolved

and suspended heavy metals and contaminate agricultural soils, thereby affecting crops and

human health. Exposure to heavy metals is known to cause kidney damage; bone fracture;

reproductive failure and infertility; damage to nervous and immune system; DNA damage or

cancer development and sperm damage, birth defects and miscarriages in humans. As such,

monitoring of heavy metals in the environment is essential to safeguard ecosystem and human

health. The Australian and New Zealand Environment and Conservation Council have

established guidelines for heavy metals in raw water to be supplied for irrigation, stock and

domestic supply (see ANZECC & ARMCANZ, 2000).

Until recently there were no reliable and time integrated techniques to assess the heavy metal

concentrations in water which could be used to assess the risk levels with respect to ANZECC &

ARMCANZ (2000) water quality guidelines. Recently, Professor Wu and his team members (see

Wu et al, 2007) developed an ‘Artificial Mussel’ technology to monitor five different heavy metals

in water. This new device is a cost effective monitoring tool which can provide a time-integrated

concentration of metals in the aquatic environment during the deployment period. Advantages of

passive sampling techniques have been proven as applied in collaborative project studying

pesticide residues in G-MW channels and reference sites (Rose and Kibria 2006).

One of the significant business risks for G-MW is the water that G-MW supplies to its customers.

It is known that many of the catchments in which G-MW operates are heavily mineralized, as

evidenced by the historical and current mining activities in these catchments. EPA has reported

elevated arsenic and cadmium levels in the Loddon catchment, and the potential for

bioaccumulation of mercury in Lake Eildon as a result of historical gold mining upstream.

G-MW has a duty of care to ensure that the water it supplies to customers is fit for purpose. As a

sustainable water authority, it is also obliged to adapt risk mitigation measures to reduce or

minimize any impacts of pollutants (such as heavy metals) on biodiversity, irrigation water, and

drinking and recreation water quality and natural water course downstream of channels and drain

outfalls. The current work was undertaken to trial the use of new “artificial mussels” technology

for heavy metals monitoring in G-MW water supply systems as a pilot study during 2007-2008

irrigation seasons.

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5. Scope of the work

Goulburn-Murray Rural Water Corporation (G-MW) signed an international collaborative

research agreement between the City University of Hong Kong, China (CityU), and the

Department of Primary Industries (DPI) (Environmental Chemistry and Health) in 2007 to trial

artificial mussel’s techniques to monitor heavy metals in some selected G-MW irrigation channels

sites as a pilot project. Under this R&D agreement, CityU was responsible for supplying artificial

mussels (AM), analyzing AM for heavy metals (Cd, Cu, Cr, Hg, and Zn) and providing technical

and scientific expertise and support for report and journal paper preparation. DPI provided

support in sampling design, spot water analysis, assistance in report and journal paper

preparation.

6. Objectives

� To test new and innovative ‘artificial mussel’ technology (passive sampling) for

heavy metals monitoring in G-MW water supply systems (stage I).

� To evaluate the use of “artificial mussel” as a tool for future monitoring of heavy

metals in wider Victorian water supply systems (stage II) .

7. Study description

7.1 : Heavy metals monitoring strategy Traditional monitoring of heavy metals in the aquatic environment involves determining and

comparing metals in water, sediment and biota but each method has its own problems and

limitation. For example, there can be large temporal variations in metal concentrations in water,

which often require frequent sampling and analysis that are not cost effective. Bio-monitoring has

been used extensively to monitor metals in the last two decades, the notable example of which is

the global “mussel watch” program (see Monirith et al. 2007). However, the metal concentration in

bio-monitors is significantly affected by physical and biological factors and restricted natural

distributions often prevent direct comparison between different biomonitoring species in different

geographical/hydrographical regimes. Furthermore, in many environments, bivalves cannot

survive because of adverse or unsuitable environmental conditions. The ‘Artificial mussel’ (AM)

(Figure 1 and 2) is a passive sampling device that can take up and release metals in a similar

fashion to live mussels under laboratory conditions (see Table 1 for a comparison of sampling of

heavy metals by spot sampling, bioindicators and artificial mussel technology and see Box 1 about

AM technology and how it works). The current work is part of ‘global artificial mussels watch

program’ being run in eight countries including Australia (see Figure 3).

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Table 1 : A comparison of sampling of heavy metals by different techniques

Heavy metals sampling Remarks

A. Spot sampling • Snap shot

• Requires frequent sampling

• Time consuming

• Costly

• Determines total metals but not-bioavailable or toxic fractions

B. Biomonitoring (live mussels) • Require killing of animals

• Metals accumulation affected by abiotic and biotic factors

• Require translocation of mussels from lab to field or local mussel species

• No standard mussels species are available worldwide

• Require complex analysis of biological samples

• Uptake both bio-available and toxic fractions

C. Artificial mussels (AM)

technology

• Continuous monitoring

• No power or energy required

• Metal accumulation/uptake not affected by biotic and abiotic factors

• A standard toll for all waters worldwide (fresh, sea, recycled/waste water)

• AM can be placed where bio-indicator organisms are not available

• Simple to handle, deploy and retrieve

• Simple to analyse

• Uptake both bio-available and toxic fractions

BOX : 1 : Artificial mussel technology and how it works?

The ‘Artificial mussel (AM)’ passive sampling is a device that collects or accumulates pollutants (heavy metals or HM)

independently through a diffusion barrier onto a sorbent medium. The device (AM) consists of non permeable Perspex

tubing (60 mm x 25 cm ) in which 200 mg Chelex-100 (50-100 mesh from Bio-Rad) is suspended in 8 mL

seawater/freshwater inside the tubing (see Figure 2). Both ends of the tubing were further capped by a layer of

polyacrylamide gel (thickness: 1 cm), to protect the gel from possible mechanical damages (Figure 1 and 2). Water

diffuses through the polyacrylamide gel into the chelax-100 (metal binding agent) and the metals are extracted

(complexed) (see Figure 2). After several weeks, the chelating agent is sampled to determine its metal content.

Figure 1 : ‘Artificial mussels’ device used in heavy metals Figure 2 : A schematic diagram showing the design of artificial mussel

monitoring (photo by Golam Kibria) chemical structure of chelex-100 is shown in the inset (Wu et al. 2007)

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Figure 3 : Artificial mussel watch program being run in eight countries including Australia.

7.2 : Monitoring sites

Artificial mussels were deployed at five selected sites from November 2007 to April, 2008 within

the G-MW region located in North Victoria, Australia (see Figure 4). Two of these sites were river

off-take for the Goulburn River (Goulburn weir, Nagambie) and Murray River (Burramine,

Yarrawonga) (reference sites). The other three sites included were Shepparton (intensive orchard),

Mooroopna (u/s : orchards, & tomatoes; d/s : outfall) and Kerang (u/s : mixed farming; d/s raw

town supply) (see Table 2)

7.3 : Monitoring schedule

7.3.1 : Sampling frequency

Deployment and retrieval : every four weeks @ 5 replicate at each site

Duration of monitoring : November 2007- April 2008 (see Table 3)

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Figure 4 : Location of five monitoring sites

Burramine-2

Shepparton-3

Mooroopna - 4

Kerang -1

Nagambie - 5

Table 2: Description of heavy metals monitoring sites for the pilot study (2007-08)

Site number & Irrigation Area Active region Location and GPS Prime targets Comments

1-Torrumbarry Irrigation area (TIA)

Kerang town Channel 14/2,

regulator-last regulator

of 14/2, 1km upstream of

Loddon-Murray Water

channel off-take

Access Rd : Collins Rd-

Bendigo HW

Town supply u/s : pasture

d/s : raw town supply

2- Murray Valley IA (MVIA)

Burramine

Channel-Yarrawonga

Main

8 mile regulator,

Occupational bridge

(Burramine Rd-MV

Highway), 20km North

from Cobram

Channel off-take for

Murray system

Murray River off-take

u/s :pasture, crop

d/s : Murray Valley

Irrigation Area

3 -Shepparton Irrigation Area (SIA)

Shepparton

Channel 12,

below Fingerboards

regulator (asset number

ST45682).

Intensive Orchards

(stone & pome fruit)

u/s : intensive orchards

d/s : pasture,

(horticulture, crops,

stock & domestic)

4-Central Goulburn Irrigation Area (CGIA)

Mooroopna

Channel 15/6/4

Ebbots regulator, Scada

1564,

Channel outfall u/s : channels of

Murchison, Toolamba,

Ardmona pass through

orchards, tomatoes and

pastures dairy

d/s :outfall to Goulburn

River

5- Goulburn weir

Nagambie Stuart Murray Canal

Goulburn Weir

Channel off-take for

Goulburn System

Goulburn River off-take

Reference site- d/s water

supply to CG, S, R-C,

PH-B irrigation area

u/s : vineyards,

tomatoes,, pasture, crop,

fish farms

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Table 2 : Date of deployment and retrieval of artificial mussel during 2007-08

Sampling

period

Sampling date Artificial mussel (AM)

1 14 & 15 November 2007 Deployment of 5 fresh AM at each site

2 12 & 13 December 2007 Retrieval of 5 old AM from each site

Deployment of 5 fresh AM at each site

3 9 & 10 January 2008 Retrieval of 5 old AM from each site


4 6 & 7 February 2008 Retrieval of 5 old AM from each site


5 5 & 6 March 2008 Retrieval of 5 old AM from each site


6 2 & 3 April 2008 Retrieval of 5 old AM from each site


8 : Methods

8.1 : Deployment and retrieval of artificial mussel

Field deployment and retrieval of AM followed procedures and protocols provided

by the CityU. This involves placing AM in an autoclaved/plastic basket with one AM

per basket (5 replicate at each site). The plastic basket was then submerged in

channels and river sites. Nylon rope and pulleys were attached to star pickets to

facilitate deployment and retrieval of autoclave baskets (see Figure 5)

AM deployment – step 1

AM deployment – step 2 (AM in

sampling basket )

AM deployment – step 3 ( Five AM in five baskets at each site)

AM retrieval-step 1

AM retrieval-step 2

AM retrieval-step 3

Figure 5 : Deployment and retrieval of artificial mussel

(note : personal protective clothing (PPE) (gloves, high visibility and shoe worn during deployment and retrieval process of AM

as part of occupational health and safety and quality assurance).

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Figure 6 : AM stored in Milli -Q water

8.2 : Storage of AM before deployment

AM were supplied by the CityU as

part of an international R&D

collaboration agreement between G-

MW and CityU. AM received from

Hong Kong were stored at G-MW

construction lab at room

temperature (William St, Tatura).

They were kept under milli-Q water

(deionised water) (Figure 6) until

deployment at risk sites. It is

essential to store AM fully hydrated

condition to avoid cracking of the gel supporting the top and bottom layers of AM.

8.3 : Shipment of AM to Hong Kong

Each batch of AM deployed at channels and rivers were retrieved at the end of four

weeks (28 day) intervals and sent via express air courier to Hong Kong (TNT or

Australia Post). Each AM was wrapped within a wet sponge with identification tags

included inside each whirl pack bag before shipment (the following procedures

followed).

a. Washed down the fouling organisms attached on the surface of AMs (if any),

and briefly rinsed the surface of retrieved AMs with the site water.

b. Soaked sponge/ cotton (Johnson’s pure cotton pads) with water from the site

and wrapped each individual AMs separately with the wet sponge/wet

cotton using rubber bands.

c. Placed each individual AM in a whirlpak bag (Solar-Cult cellulose Swab-

SBDCS-100-1, Arrow Scientific Pty Ltd, NSW) and then in a re-sealable bag

(Glad snap lock bag)

d. Double labelled each AM (with pencilled card inside + water proof label on

each whirlpak bag).

9. Water quality

9.1 : Water temperature

Surface water temperature of each site was recorded using a fractional degree

thermometer (405 mm blue LO-tox TM filled) during retrieval of AM. Lowest

temperatures was recorded in April and highest in January (see Table 3)

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Table 3 : Water temperature of the five monitoring sites

November/07 December/07 January/08 February/08 March/08 April/08

Site 1 : Kerang (T)

Mixed farming

19.2

18.9

17.1

17.8

21.5

21.0

21.1

21.2

18.9

19.0

15.6

15.8

Average 19.0 17.4 21.2 21.2 19.0 15.7

Site 2 : Burramine (MV)

Reference-Murray Rive off take

26.2

25.8

27.1

27.8

29.5

29.2

27.1

27.3

24

24

17.0

16.9

Average 26.0 27.4 29.4 27.2 24.0 17.0

Site 3 : Shepparton (S)

orchards

24.3

24.0

20.8

21.0

25.2

24.7

21.8

21.8

20.2

20.3

14.0

14.1

Average 24.2 20.9 25.0 21.8 20.2 14.0

Site 4 : Mooroopna (CG)

orchards and tomatoes

21.8

22.4

20.8

21.0

24.8

25.0

21.4

21.2

20.5

20.8

13.5

13.8

Average 22.1 20.9 24.9 21.3 20.6 13.6

Site 5 : Nagambie (GW)

Goulburn River off take

26.2

26.3

22

23

23

23.2

21

21.2

21.5

21.4

17.5

18

Average 26.2 22.5 23.1 21.1 21.4 17.8

9.2 : Water Hardness

Water hardness of each site was measured using Hatch water quality test strips (Cat

27452-50, Hatch Company Loveland, CO, USA). Water hardness varies from 50 mg/L

to 120 mg/L (see Table 4). The procedures followed is as follows:

• dip the strip into water for 1 second

• shake off excess water

• compare the total hardness test pad with the colour chart

Table 4 : Water hardness (mg/L) of the five monitoring sites (January-April 08)

January/08 February/08 March/08 April/08 Comments

Site 1 : Kerang

Mixed farming

120 120 120 120 Very hard

Site 2 : Burramine

Reference-Murray River

25 50 50 50 Moderate to

slightly hard

Site 3 : Shepparton

Intensive orchards


slightly hard

Site 4 : Mooroopna

orchards and tomatoes


very hard

Site 5 : Nagambie

Reference - Goulburn River


hard

The following classification was used to classify water hardness

Soft : 0 - 20 mg/L as calcium ; Moderately soft : 20 - 40 mg/L as calcium ; Slightly hard : 40 - 60 mg/L as calcium ; Moderately hard : 60

- 80 mg/L as calcium; Hard : 80 - 120 mg/L as calcium; Very Hard : >120 mg/L as calcium

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Figure 6 : Ladder was installed on a steep site to prevent injury (site 5)

10 . Analytical techniques

The contents of each individual AM were emptied into a sintered glass filter

followed by eluting two times with 12.5 mL 6 M HNO3 (analytical grade). The

elutriant was made up to a known volume with deionized double distilled water.

The concentrations of Cd, Cr, Cu, Pb and Zn were determined by flame atomic

absorption spectrophotometry (FAAS; Shimadzu 650IS) and inductively- coupled

plasma atomic emission spectrometry (ICP-AES; Perkin Elmer Plasma 1000).

Concentration of metals in the AM was expressed in terms of µg/g of Chelex. The

analysis was done at the City University of Hong Kong.

11 : Quality Assurance

Five replicate AM were deployed at each site to assess the variability in accumulation

of heavy metals within a site. AM were analyzed by a professional chemist (one of

the author -Alice KY Chan) from the CityU. To reduce any contamination either

during deployment and retrieval, gloves and protective clothing was worn (see

Figure 5). AM retrieved were sent to Hong Kong via fast air courier.

12 : Occupational health and safety

A site specific risk assessment was conducted, and a safe work instruction (risk

control measures) was developed for all the 5 sampling sites (Figure 6).

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13. Results

The artificial mussels (AM) deployed in G-MW channels and rivers had accumulated

both targeted and non-targeted metals. The targeted metals are cadmium, copper,

mercury and zinc. In addition, AM also accumulated some non-targeted metals such

as chromium, cobalt, iron, and nickel. The AM results showed both spatial and

temporal variations between and within the monitoring sites (see Figures 7 to 13).

The order of accumulation of metals in AM were as follows :

• Targeted metals : Zn>Cu>Cd>Hg

• Non-targeted metals : Fe>Ni>Co>Cr

The metals detected in AMs (min-max) are given in Table 5.

Table 5 : Range of metals detected in artificial mussels (min-Max) in AMs (µµµµg/g) during

December 2007-March 2008 at different sites [Note : This table should be followed in conjunction

of Figures 7 to 13].

Reference –

Murray River

(Burramine- site

2

Irrigation channel

site (Kerang-

Murray system-

site 1)

Reference –

Goulburn River

(Nagambie - site 5)

Irrigation channel

site (Shepparton -

Goulburn system-

site 3)

Irrigation channel

site (Mooroopna -

Goulburn system-

site 4)

Cadmium (Cd) <1.0-1.3 <1.0-1.5

<1.0-1.3 <1.0-1.3 <1.0-1.1

Chromium (Cr) <1.0-2.3 <1.0-2.9 <1.0-2.0 <1.0-2.3

<1.0-2.0

Cobalt (Co) 1.4-6.1 1.4-2.8 1.0-2.0 1.0-2.4

<1.0-5.4

Copper (Cu)

6.3-24.3 6.0-55.6 <1.0-132.3 6.5-22.3 2.9-30.4

Iron (Fe) 11.3-728.5 8.8-31.4 8.6-165.0 9.9-33.4

8.7-39.4

Mercury (Hg) < 0.60 < 0.60 < 0.60 < 0.60 < 0.60

Nickel (Ni) 1.5-6.4

1.0-13.6

<1.0-4.0

1.1-12.9

<1.0-10.2

Zinc (Zn) 10.9-37.3

10.5-54.8

12-90.6

14.0-36.6

5.1-34.1

14. Discussion

Using AMs comparisons on both a temporal and a spatial basis can be made for

chromium (Figure 8), copper (Figure 10), nickel (Figure 12) and zinc (Figure 13).

Nickel and chromium showed similar monthly trends in Kerang to Burramine

(Burramine is Murray River reference site) as did Shepparton and Mooroopna in

comparison to Nagambie (Nagambie is Goulburn River reference site). This

demonstrated that there were no AM available nickel or chromium inputs or

mobilisations in the irrigation channel area relative to reference sites during the 2007-

08 seasons. In contrast, AM available copper levels at Kerang were significantly

higher than Burramine (Murray River reference site) in February 2008 suggesting

19

localised inputs or mobilisations of copper. At Shepparton and Mooroopna, the AM

available copper was significantly higher in January and February 2008 respectively

than Nagambie (Goulburn River reference site) indicating an increase in AM

available copper in comparison with Nagambie. Very high levels iron (Figure 11)

was detected at the two reference sites. For example, iron concentrations in

Burramine in March and Nagambie in January were significantly higher compared to

sites located within irrigation areas which may suggest external iron inputs in the

irrigation areas during that period (Figure 11). Temporal comparisons of cadmium

show that in February levels may have been generally higher at all sites (see Figure 7)

whereas cobalt shows similar trend at all five sites (see Figure 9).The zinc level in

February at Kerang is significantly higher than at Burramine indicating local inputs

or mobilisation of zinc (Figure 13).In all AM samples the mercury level was below

the detection limit of (0.6 µg/g).

The metals accumulated in AMs could be a source of natural or a source of fertilisers

and pesticides used in the irrigation areas during the monitoring periods, for which

G-MW don’t have any control. As there were no freshwater calibration and

concentration factors for AMs were available therefore results cannot be compared

with ANZECC & ARMCANZ (2000) guideline thresholds values for the protection of

aquatic ecosystems or water quality. Further, metals detected in AMs are in artificial

irrigation channels where aquatic ecology is not protected (see EPA Victoria 2003).

15. Conclusion

This pilot project verified novel artificial mussel (AM) technology for monitoring

heavy metals in waterways for the first time in Australia. The ability to deploy and

retrieve AMs in selected risk areas and analyse and interpret AM results was

confirmed for five sites within Goulburn-Murray Water Irrigation Areas. The study

found that artificial mussel (AM) technology was a very reliable passive sampling

(continuous monitoring) tool for monitoring of heavy metals in G-MW waterways as

it detected all the targeted metals as well as some non-targeted metals. However, as

the pilot trial was for a very short period and covered only few sites therefore it is

suggested to extend the program to cover the wider G-MW catchments (six irrigation

areas) for the two irrigation seasons. And it is further suggested that the extended

study should cover some outside risk sites for data comparison and testing of the

AM technology such as Melbourne Water/Yarra Catchments and North Central

CMA. As Australia is facing increasing water shortages due to the effects of climate

change and ongoing drought, the suitability of other water resources needs to be

assessed. In this respect, AM technology could be a useful and reliable risk

assessment tool for assessing recycled waters, bore water and wastewaters for

example.

20

Burram

ine (site

1-referen

ce m

urray River)

0

0.2

0.4

0.6

0.81

1.2

1.4

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Mon

ths

Concentrations (mg/kg)

Kerang (site 1-mixed farming)

0

0.2

0.4

0.6

0.81

1.2

1.4

1.6

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


CA

DM

IUM

in

AM

Nag

ambie (site

5 -referen

ce Gou

lburn riv

er)

0

0.2

0.4

0.6

0.81

1.2

1.4

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Mon

ths


Shepparton (site 2-orchards)

-0.20

0.2

0.4

0.6

0.81

1.2

1.4

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Mooroopna (site 4-orchards & tomatoes)

0

0.2

0.4

0.6

0.81

1.2

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Fig

ure

7

: F

ou

r w

eek

av

era

ge c

ad

miu

m (

Cd

) co

nce

ntr

ati

on

s in

art

ific

ial

mu

ssel

s (µ

g/g

dry

wei

ght;

mea

n(±

S.E

.M)

for

each

dep

loy

men

t p

erio

d a

t re

fere

nce

sit

es v

ersu

s

imp

act

ed s

ite

(av

era

ge o

f 5

rep

lica

tes

at

each

sit

e). M

on

ths

wit

ho

ut

a b

ar

ind

ica

te c

on

cen

tra

tio

ns

lev

els

wer

e b

elo

w L

oR

(<

1.0

mg/

kg)

.

21

Burram

ine (site 2- reference Murray River)

0

0.51

1.52

2.5

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Kerang (site 1- M

ixed farm

ing)

0

0.51

1.52

2.53

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Mon

ths


CH

RO

MIU

M i

n A

M

Nagam

bie (site 5-reference Goulburn River)

0

0.51

1.52

2.5

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months



0

0.51

1.52

2.5

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months



0

0.51

1.52

2.5

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Fig

ure

8 :

Fo

ur

wee

k a

ver

age

ch

rom

ium

(C

r) c

on

cen

tra

tio

ns

in a

rtif

icia

l m

uss

els

(µg/

g d

ry w

eigh

t; m

ean

(±S

.E.M

) fo

r ea

ch d

eplo

ym

ent

per

iod

at

refe

ren

ce s

ites

ver

sus

imp

act

ed s

ite

(av

era

ge o

f 5

rep

lica

tes

at

each

sit

e). M

on

ths

wit

ho

ut

a b

ar

ind

ica

te c

on

cen

tra

tio

ns

lev

els

wer

e b

elo

w L

oR

(<

1.0

mg/

kg)

.

22

Burram

ine (site 2 -referenec Murray River)

0

0.51

1.52

2.53

3.54

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Mon

ths


Kerang (site 1 -mixed farming)

0

0.51

1.52

2.53

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


CO

BA

LT

in

AM

Nagambie ( s

ite 5-referen

ce Gou

lburn River)

0

0.51

1.52

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Mon

ths



0

0.51

1.52

2.5

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months



0

0.51

1.52

2.53

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months

Concentration (mg/kg)

Fig

ure

9 :

Fo

ur

wee

k a

ver

age

co

ba

lt (

Co

) co

nce

ntr

ati

on

s in

art

ific

ial

mu

ssel

s (µ

g/g

dry

wei

ght;

mea

n(±

S.E

.M)

for

each

dep

loy

men

t p

erio

d a

t re

fere

nce

sit

es v

ersu

s im

pa

cted

site

(a

ver

age

of

5 re

pli

cate

s a

t ea

ch s

ite)

. Mo

nth

s w

ith

ou

t a

ba

r in

dic

ate

co

nce

ntr

ati

on

s le

vel

s w

ere

bel

ow

Lo

R (

< 1.

0 m

g/k

g).

23

Burramine (site 2 - Reference Murray River)

05

10

15

20

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Kerang (site 1-mixed farm

ing)

024681012141618

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Mon

ths


CO

PP

ER

in

AM

Nagam

bie (site 5-Reference Gou

lburn River)

0510152025

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Mon

ths


Shepp

arton (site 3 -intensive orchards)

02468101214161820

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Mon

ths


Mooroopna (site 4 - orchards & tomatoes)

0510152025

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Fig

ure

1

0 :

Fo

ur

wee

k a

ver

age

co

pp

er (

Cu

) co

nce

ntr

ati

on

s in

art

ific

ial

mu

ssel

s (µ

g/g

dry

wei

ght;

mea

n(±

S.E

.M)

for

each

dep

loy

men

t p

erio

d a

t re

fere

nce

sit

es v

ersu

s im

pa

cted

site

(a

ver

age

of

5 re

pli

cate

s a

t ea

ch s

ite)

. Mo

nth

s w

ith

ou

t a

ba

r in

dic

ate

co

nce

ntr

ati

on

s le

vel

s w

ere

bel

ow

Lo

R (

< 1.

0 m

g/k

g).

24

Burramine (site 2 - reference Murray River)

0

50

100

150

200

250

300

350

400

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Kerang (site 1 - mixed farm

ing)

05

10

15

20

25

30

35

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


IRO

N i

n A

M

Nagambie (site 5 - Reference Goulburn River)

0

10

20

30

40

50

60

70

80

90

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Shepparton (site 3- intensive orchards)

05

10

15

20

25

30

35

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Mooroopna (site 4 - orchards and tomatoes)

051015202530

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Fig

ure

11

: F

ou

r w

eek

av

era

ge i

ron

(F

e) c

on

cen

tra

tio

ns

in a

rtif

icia

l m

uss

els

(µg/

g d

ry w

eigh

t; m

ean

(±S

.E.M

) fo

r ea

ch d

eplo

ym

ent

per

iod

at

refe

ren

ce s

ites

ver

sus

imp

act

ed

site

(a

ver

age

of

5 re

pli

cate

s a

t ea

ch s

ite)

.

25

Burramine (site 2- reference Murray River)

0123456

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months



ing)

012345

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months

Concentartions (mg/kg)

NIC

KE

L i

n A

M

Nagam

bie (site 5-reference Goulburn River)

0123456

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Shepp

arton (site 3-orchards)

012345678

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Mon

ths



01234567

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Fig

ure

1

2 :

Fo

ur

wee

k a

ver

age

nic

kel

(N

i) c

on

cen

tra

tio

ns

in a

rtif

icia

l m

uss

els

(µg/

g d

ry w

eigh

t; m

ean

(±S

.E.M

) fo

r ea

ch d

eplo

ym

ent

per

iod

at

refe

ren

ce s

ites

ver

sus

imp

act

ed

site

(a

ver

age

of

5 re

pli

cate

s a

t ea

ch s

ite)

.

26

Burramine (site 2 - reference Murray River)

05

10

15

20

25

30

35

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months



ing)

05

10

15

20

25

30

35

40

45

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


ZIN

C i

n A

M

Nagambie (site 5 - reference Goulburn River)

0

10

20

30

40

50

60

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Shepparton (site 3 - intensive orchards)

05

10

15

20

25

30

35

40

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Mooroopna (site 4 - orchards & tomatoes)

05

10

15

20

25

30

35

40

45

Dec-07

Jan-08

Feb-08

Mar-08

Apr-08

Months


Fig

ure

13

: F

ou

r w

eek

av

era

ge z

inc

(Zn

) co

nce

ntr

ati

on

s in

art

ific

ial

mu

ssel

s (µ

g/g

dry

wei

ght;

mea

n(±

S.E

.M)

for

each

dep

loy

men

t p

erio

d a

t re

fere

nce

sit

es v

ersu

s im

pa

cted

site

(a

ver

age

of

5 re

pli

cate

s a

t ea

ch s

ite)

.

27

16. References

Australian and New Zealand Environment and Conservation Council (ANZECC) and

Agriculture and Resource Management Council of Australia and New Zealand

(ARMCANZ), (2000).Australian and New Zealand Guidelines for Fresh and Marine Water

Quality, Volume 1, The Guidelines (Chapters 1-7).

EPA (2003). State Environment Protection Policy (Waters of Victoria) : Policy Impact

Assessment. Southbank, EPA, Victoria. EPA Publication no 905, 91p

Monirith, I., Ueno, D., Takahashi, S., Nakata, H., Sudaryanto, A., Subramanian, A.,

Karuppiah, S., Ismail, A., Muchtar, M., Zheng, J., Richardson, B.J., Prudente, M., Hue, N.D.,

Tana, T.S., Tkalin, A.V., and Tanabe, S. 2003. Asia-Pacific mussel watch : monitoring of

persistent organochlorine compounds in coastal waters of Asian countries. Marine Pollution

Bulletin. 46 : 281-300.

Rose G. and Kibria G. 2006. Pesticide monitoring in Goulburn-Murray Waters Irrigation

Supply Channels covering the six irrigation areas [2004-2006 irrigation season study report].

Department of Primary Industries, State of Victoria and Goulburn-Murray Rural Water

Authority (G-MW), Tatura. 43p. (http://www.g-mwater.com.au/downloads/PESTICIDE_2004_2006_REPORT.PDF)

Wu, RSS, Lau, TC, Fung, WKM, Ko, PH and Leung, KMY (2007) An artificial mussel for

monitoring heavy metals in a marine environments. Environmental pollution, 145, 104-110.

17. Appendix

28

Abstract of paper presented at the13th Australasian Society for Ecotoxioclogy, 2009

‘ARTIFICIAL MUSSEL’ A NEW ENVIRONMENTAL RISK

ASSESSMENT TOOL FOR HEAVY METALS MONITORING IN

SURFACE WATRES-PILOT STUDY

Golam Kibria 1,3, Gavin Rose

2, Rudolf Wu

3, T.C. Lau

3, Christie Y. K. Lung

3, Alice KY

Chan 3

1 Goulburn Murray Rural Water Corporation (G-MW), Tatura, Victoria, Australia. [email protected] 2 Department of Primary Industries (DPI), Future Farming Systems Research Division, Werribee Chemistry

Laboratory, Victoria, Australia. [email protected] 3 Centre for Marine Environmental Research and Innovative Technology & Centre for Coastal Pollution and

Conservation, City University of Hong Kong (CityU), China. [email protected]

Heavy metals can pollute water supply systems through natural deposits, waste discharged from mining,

industrial and agricultural activities. Water contaminated with heavy metals may be unsuitable for irrigation,

human consumption, livestock watering, aquatic ecosystems protection and recreation and aquaculture . Until

recently no reliable and time-integrated (continuous) monitoring techniques to assess heavy metal

concentrations in water were available. The ‘Artificial Mussel’ (AM) passive sampling method collects or

accumulates pollutants independently through a diffusion barrier onto a sorbent medium. During the

deployment period, the AMs accumulate five different heavy metals in water. This device can be used in many

areas such as irrigation channels, rivers, recycled/wastewater ponds to monitor and assess the risk posed by

heavy metals. The current work is part of ‘global artificial mussels watch program’ being run in eight countries.

This project trialed the use of novel artificial mussel (AM) technology for monitoring heavy metals in

waterways for the first time in Australia. The ability to deploy and retrieve AMs in selected areas and analyse

and interpret AM results was confirmed for five sites within Goulburn-Murray Water Irrigation District

(including rivers and irrigation channels). AM had accumulated both targeted and non-targeted metals. The

targeted metals are cadmium, chromium, copper, mercury, and zinc, and the AMs also accumulated non-

targeted metals such as iron, cobalt, and nickel.

As Australia is facing increasing water shortages due to the effects of climate change and ongoing drought, the

suitability of other water resources needs to be assessed. These include assessing the risk from heavy metals in

recycled water and treated wastewaters. An expanded study is being planned in Victoria involving Goulburn

Murray Rural water Corporation (G-MW), City University of Hong Kong (CityU), the University of Hong

Kong (HKU), DPI (Werribee, Queenscliff), Melbourne Water and North Central CMA to monitor heavy metals

in selected sites across northern and central Victorian catchments using artificial mussels.

monitoring heavy metals in goulburn-murray … · department of biology and chemistry, city...

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