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Environmental Pollution 132 (2004) 355e363

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A retrospective assessment of gold mining in the Reedy


Creek sub-catchment, northeast Victoria, Australia:
residual mercury contamination 100 years later
R.C. Churchill*, C.E. Meathrel, P.J. Suter
Department of Environmental Management and Ecology, La Trobe University, Wodonga, Victoria, Australia 3690
Received 27 March 2003; accepted 5 March 2004

Capsule: Surface water Hg concentrations can exceed government guidelines.


Abstract
The mining of gold can lead to toxic metals such as mercury (Hg) contaminating watercourses as by-products. The Reedy Creek
sub-catchment, in northeast Victoria, Australia, was mined for gold in the 1850s. In 1998, samples were taken from six watercourses
to measure any remaining toxic metal contamination in sediments and surface waters from two creeks with no previous gold mining
(controls) and four that were mined. Although mean concentrations of Hg (measured using an ICP-OES) in sediments were below
worldwide background levels, individual sites along Reedy Creek had slightly elevated Hg concentrations. In contrast, the Hg
concentrations in the surface waters were above background levels. Temporal uxes of very high Hg concentrations in the surface
waters during periods of rst ow and ood events revealed that Hg concentrations in the surface waters may, at certain times of the
year, exceed all Australian and New Zealand Environment and Conservation Council (National Water Quality Management
Strategy. Australian Water Quality Guidelines for Fresh and Marine Waters, ANZECC, 2000a) guidelines for water use and the
protection of the aquatic ecosystem.
2004 Elsevier Ltd. All rights reserved.
Keywords: Water quality; Retrospective assessment; Gold mining; Mercury (Hg); ICP-OES

1. Introduction
The concentration of trace elements, particularly
heavy metals, in stream sediments and in surface waters
may reect the occurrence and abundance of these
metals in the surrounding soil (deGroot et al., 1982).
Anthropogenic activities can result in the heavy metal
uxes equalling or exceeding the amounts released under
natural weathering conditions. It has been suggested
that metals derived from anthropogenic activities are
less eectively bound to particulate matter compared
with those derived from natural processes and therefore

* Corresponding author. Present address: Environmental Protection


Agency, Corner Wood and River Streets, Mackay, Queensland,
Australia 4740. Fax: C61-7349447836.
E-mail address: ricci.churchill@epa.qld.gov.au (R.C. Churchill).
0269-7491/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2004.03.001

will remobilise more readily following physico-chemical


variability of the water system (Reuther, 1992).
In the clay fraction of the soil prole an enrichment of
Hg may occur due to the strong bonds formed between
Hg and the negatively charged clay surfaces, while many
other less strongly bonded elements are leached and
become depleted (Andersson, 1979). The physico-chemical conditions vary widely between dierent sediment
types and between dierent horizons, and as a result the
Hg content may change with sediment depth.
Sediments worldwide have been shown to contain a
range of Hg concentrations from 0.01 to 0.3 mg kg1
(Jones and Jarvis, 1981). The east coast of Australia is in
a mercuriferous zone; thus a river draining this region
may contain higher background levels of Hg than rivers
draining non-mercuriferous areas (Hart, 1982). Mercury
is considered to be the most toxic metal found in the
freshwater environment (Hellawell, 1986). Freshwater

R.C. Churchill et al. / Environmental Pollution 132 (2004) 355e363

has been shown to contain natural background Hg concentrations usually below 0.03 mg l 1 (Beaton, 1998).
Like many other industries, gold mining has led to
the generation of large quantities of waste materials
during the extraction processes and in tailings. The
mining of metals has been reported to adversely aect
aquatic ecosystems in several ways, such as the contamination of surface waters, ground waters and aquatic
sediments (Galbraith et al., 1972; Moore et al., 1979),
the accumulation of toxic metals in aquatic organisms
(Nehring, 1976) and the alteration of sh and macroinvertebrate community structure (LaPoint et al., 1984).
Mining operations are associated with a wide range
of environmental problems and contamination within a
catchment usually continues long after mining operations have ceased (Johnson and Eaton, 1980).
In Australia, Hg use peaked during the gold rush in
the 1850s. Mercury was used in the amalgamation process to extract gold from quartz rock. Several studies
have demonstrated the environmental persistence of Hg
from past gold mining activities (Glover et al., 1980;
Bycroft et al., 1982; Ealey et al., 1983). Wise (1966, cited
in Bycroft et al., 1982) estimated that the weight of Hg
consumed in the amalgamation process was of the same
order of magnitude as the weight of gold recovered.
Hence, the present potential for Hg contamination is
high. Katz (1972) estimated that hundreds of years are
required for the natural decontamination of Hg polluted
environments.
Signicant Hg concentrations are contained in the
tailings of amalgamation operations from past gold
mining activities (Gale et al., 1973; Bycroft et al., 1982).
Even though it has been many years since most Australian gold mines ceased operation, tailing dumps still
exist. Mercury concentrations of 0.04e0.09 mg kg1
were recorded from tailings of an abandoned gold mine
on the Thompson River, Victoria (Melbourne and
Metropolitan Board of Works, 1975). In addition,
tailings from a mine site near Woods Point, Victoria,
have been found to contain up to 0.088 mg kg1 Hg
(Bycroft et al., 1982). Tailings were often used to stabilize
eroding creek beds and therefore present a potential
source for the continuing release of Hg into adjacent
water bodies (Bycroft et al., 1982). Bycroft et al. (1982)
found high levels of Hg in the river sediments and biota
that was a result of gold mining in the Lerderderg River
catchment in Victoria 50 years earlier.
Reedy Creek in northeast Victoria was mined for
gold in the 1850s. Amalgam has been found in the creek
below Woolshed Falls (sites 4 and 5) and there is local
concern about the potential hazard of Hg contamination. The objectives of this study were designed to address these concerns by determining if Hg was still
present in the sediments and surface waters of the Reedy
Creek sub-catchment 100 years after large-scale mining
ceased.

2. Materials and methods


2.1. Study sites
Five creeks and a pond in the Reedy Creek subcatchment, northeast Victoria, were selected to identify
the eects of Hg contamination from past and present
land practices (Fig. 1). Two creeks on Mount Pilot
(Snake Head and Old Hands), which were not mined for
gold, were chosen as controls. Three sites were sampled
in each creek. Three creeks and a dam that were subjected to gold mining in the 1850s, Hurdle, Spring and
Reedy Creeks and Gold Dredge Dam, were selected to
represent water bodies likely to be aected by mining.
The number of sites per creek diered depending
on the accessibility, level of impact and creek length
(Table 1). Hurdle Creek had two sampling sites, Spring
Creek had three and Reedy Creek had nine. In addition,
one site at the disused Gold Dredge Dam, in Eldorado
(40 km downstream from Beechworth) was also
sampled.
Sampling occurred between March and August 1998.
The sediments were sampled only once while the surface
waters were sampled three times to allow for seasonal
variations in ow.
All samples were collected in acid-washed, highdensity, polypropylene jars. All glassware and other
utensils required for sample collection and analyses were
soaked overnight in a detergent bath containing 5%
Extran, then rinsed thoroughly in water before being
immersed in an acid bath (5% HCl) to prevent any
contamination.

0.04

0.03
Mercury (mg kg-1)

356

Sediment
profile

0.02

Top
0.01
Middle
0.00

Bottom
SH

OH

SC
HC
Creek

RC

GD

Fig. 1. Map of the Reedy Creek sub-catchment in northeast Victoria,


Australia, examined for residual mercury almost 150 years after
mining. Star symbols denote control sites that were not mined
(SH = Snake Head Creek, OH = Old Hands Creek) while the circle
symbols denote sites that were all subjected to gold mining (numbers
1e9 = Reedy Creek, HC = Hurdle Creek, SC = Spring Creek,
GD = Gold Dredge Dam). Scale bar is 10 km.

R.C. Churchill et al. / Environmental Pollution 132 (2004) 355e363


Table 1
Details of sampling locations examined for residual mercury almost
150 years after mining in the Reedy Creek sub-catchment, northeast
Victoria
Controls
Snake Head Creek (SH)
Site 1
Second turn off into State Park on
Old Coach Road
Site 2
First turnoff into State Park on
Maginness Road
Site 3
Bridge on Beechworth Road
Old Hands Creek (OH)
Site 1
Intersection of Maginness Road and
Wooragee Road
Site 2
Spring on Maginness Road
(after dam on right)
Site 3
Very end of last dirt track
Impacted
Hurdle creek (HC)
Site 1
Track off Stanley Road above
Lake Kerford
Site 2
Road off Stanley Road below
Lake Kerford
Spring Creek (SC)
Site 1
Waterfalls under bridge on
Ford St (no safe access)
Site 2
Bridge on Gorge Scenic Drive
Site 3
First bridge on McFeeters Road
Reedy (Reids) Creek (RC)
Site 1
Bridge on BeechwortheWangaratta
Road
Site 2
Bridge on ChilterneBeechworth Road
Site 3
Above Woolshed Falls on McFeeters
Road
Site 4
Picnic area on Woolshed Road
Site 5
Crossing between McFeeters Road and
Woolshed Road
Site 6
Third track on right after Wornes Track
on Woolshed Road
Site 7
Byrne Gully Road off Woolshed Road
Site 8
Crossing on Woolshed Road
Site 9
First bridge past Eldorado on Woolshed
Road
Gold Dredge Dam
Site 1
Approx 100 m around from dredge on
dirt track

SH1
SH2
SH3
OH1
OH2
OH3

HC1
HC2

SC1
SC2
SC3
RC1
RC2
RC3
RC4
RC5
RC6
RC7
RC8
RC9

GD1

Replicates were analysed to ensure the quality of


the assay. Also, blanks, spiked samples and standard
solutions were analysed at the beginning of each batch
of samples to ensure accuracy and precision of the
analyses.
For each assay the standard solutions were prepared
in the same matrix as the samples. A range of standards
between 2 and 0.2 ppm were prepared for Hg analysis.
Each sample was analysed for Hg using an inductively coupled plasma optical emission spectrophotometer (ICP-OES). The ICP-OES primary wavelength
used was 184.950 nm. The detection limits of the ICPOES for Hg were between 0:01e2:4 G 0:01 mg kg1 for
sediment and 0:01e2:4 G 0:01 mg l1 for surface waters.

357

2.2. Sediment analysis


Sediment samples were collected from the creek beds
in March 1998 while the creeks were relatively dry using
a corer and shovel. Three zones (top, middle and bottom) were sampled from a sediment core collected at
each site. Three replicate core samples were collected
from each soil zone at each site. The top zone was at the
surface of the creek bed (0e5 cm in depth) and included
organic matter, silt and sand. The middle zone was
between 10 and 30 cm beneath the surface samples and
consisted mainly of gravel and sand. The bottom zone
was taken just above the B horizon and was usually
40e60 cm below the creek bed. At several sites there was
only a top layer overlying granite bedrock, therefore
only three top samples were taken.
Whole moist/wet sediment samples were preserved by
dropwise addition of 5 M HNO3 to achieve a pH !2
(Franson, 1995, cited in Eaton et al., 1995). This prevented any complexation between organic matter and heavy
metals in the sample that would otherwise lead to a
reduction in the concentration of heavy metals extracted.
The preserved sediment samples were dried in a fan
forced oven set at 30 (C to avoid loss of mercury
through evaporation (deGroot et al., 1982). The length
of time required to dry samples varied, but most dried in
approximately seven days. Once dry, each sediment
sample was sieved using a roller mill. The samples were
separated into two fractions: ne (!2 mm) and coarse
(O2 mm) particulates. This provided a more representative homogeneous sub-sample from each of the ne
(sand, silt and organic matter) particulate fractions. The
coarse particulate material was not analysed as the
highest concentrations of contaminant metals were usually found in the very ne-grained sediments (deGroot
et al., 1982; Environment Protection Authority, 1984).
The Hg digestion procedure was an adaptation of the
method by Page (1982). A blank sample (without the
sediment) was also digested with each batch of 10 samples to correct for levels of Hg in the reagent.
Five standard solutions (20, 2, 0.2, 0.02 and 0.002
mg l 1) and a blank were prepared. The 20 mg l 1 Hg
standard was prepared by taking a 0.2 ml aliquot of
a 10 000 mg l 1 Hg ICP-OES standard solution, combining this with 20 ml H2SO4, 10 ml HNO3 and 4 ml
HCl to match the matrix in which the samples were
digested. The solution was diluted to a volume of 100 ml
using ultra high purication (UHP) H2O. This procedure followed sequentially for the remaining 2, 0.2,
0.02 and 0.002 mg l 1 standard solutions using 10 ml of
the previous standard in each case.
2.3. Surface water analysis
When water was present in the creeks, a sample was
taken from the centre of the creek, 5 cm below the water

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R.C. Churchill et al. / Environmental Pollution 132 (2004) 355e363

surface using a 400 ml jar. At all sampling events, water


samples were collected rst to avoid contamination from
sediment disturbance. A total of three sampling trips in
1998 were undertaken. One in May (Australian autumn,
rst ow), one in June (ood event) and one in August
(high ow).
After collection from each site, water samples were
immediately stored on ice for up to 6 h then transported
to the laboratory. In the laboratory, a 20 ml sub-sample
was removed from each sample and ltered into test
tubes through Whatman #41 lter paper to remove any
ne particulate and crystalline material and larger precipitated organic material. The water samples were then
stored for up to seven days in a refrigerator at 4 (C
before analysis (Franson, 1995, cited in Eaton et al.,
1995).
Whilst in the eld sampling the sediments and the
surface water, pH, temperature, conductivity and dissolved oxygen were measured using a HACH multiprobe. Depth, width and ow rate were also measured at
three dierent locations at each site using a ruler, tape
measure and a MiniAir anemometer, respectively. These
measurements were then averaged to provide a representative depth, width and ow for each site.
One set of ve standard solutions (20, 2, 0.2, 0.02 and
0.002 mg l 1) and a blank were prepared. The 20 mg l 1
solution was prepared from 0.2 ml of the Hg ICP-OES
standard solution and diluted to a 100 ml volume with
UHP H2O. From this solution, a series dilution followed
for the remaining standard solutions, using 10 ml of the
previous solution and diluting to a volume of 100 ml
with UHP H2O.

2.4. Statistical analysis


Comparisons between the mercury concentrations in the
sediment prole and surface waters of each creek and either
the depth or sampling trip were completed using General
Linear Models using the SPSS v.11 statistical package.
When required, one-way analysis of variance (ANOVA)
was followed by Schees a posteriori contrasting.
Pearsons correlation coecients and paired t-tests
were used to compare the mercury concentrations in the
sediments with those in the surface waters.
All statistical procedures followed Sokal and Rohlf
(1995) and all means are presented as G1 S.E. unless
otherwise stated.

3. Results
3.1. Physico-chemistry of water bodies
Table 2 presents the mean physico-chemical data for
water in each creek for the three sampling trips. Discharges were lowest in May when the streams were
reduced to a series of pools or were only just owing.
Conductivity and temperature were highest in May and
dissolved oxygen was lowest at the control sites. The
water temperature decreased and discharge rates tended
to increase through the autumn/winter months. Old
Hands Creek and the Gold Dredge Dam had the highest
conductivities. Spring and Reedy Creeks had the highest
discharge rates, coldest temperatures and highest dissolved oxygen content.

Table 2
The mean physico-chemical data G 1 S.E. for each trip and creek examined for residual mercury almost 150 years after mining in northeast Victoria,
Australia
Creek/trip

pH

SH/1
SH/2
SH/3
OH/1
OH/2
OH/3
HC/1
HC/2
HC/3
SC/1
SC/2
SC/3
RC/1
RC/2
RC/3
GD/1
GD/2
GD/3

6.91
6.95
6.98
6.90
6.91
6.99
6.98
6.92
7.00
7.05
6.96
7.05
6.98
6.99
7.06
7.04
7.01
7.08

G 0.01
G 0.00
G 0.05
G 0.03
G 0.02
G 0.01
G 0.01
G 0.01
G 0.01
G 0.01
G 0.02
G 0.02
G 0.01
G 0.01
G 0.01
G 0.01
G 0.00
G 0.00

Temperature
((C)

Conductivity
(mS cm1)

Dissolved
oxygen (mg l 1)

Depth
(m)

9.47
8.50
8.70
10.50
9.20
8.33
10.90
8.20
8.50
10.40
6.00
7.30
10.40
7.30
8.60
13.00
8.40
9.10

206.6
171.6
106.4
444.1
312.1
132.9
42.5
32.2
39.6
94.3
111.4
101.3
191.0
152.5
130.5
331.0
322.7
264.9

5.76
10.45
11.45
6.73
7.05
9.64
12.97
12.82
13.19
13.87
15.59
15.14
13.45
15.51
14.42
10.85
8.26
12.27

0.29
0.42
0.23
0.22
0.51
0.57
0.18
0.22
0.23
0.39
0.46
0.42
0.38
0.53
0.76
0.47
0.54
0.81

G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G

0.07
0.03
0.06
0.59
0.23
0.22
0.17
0.37
0.46
0.20
0.30
0.33
0.14
0.20
0.10
0.03
0.02
0.03

G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G

1.1
4.3
4.1
44.4
76.8
34.2
5.8
8.0
5.2
8.1
7.2
4.3
13.9
3.8
2.1
1.2
1.1
1.7

G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G

0.17
0.16
0.18
2.06
1.38
0.72
0.42
0.76
1.07
0.32
0.19
0.18
0.33
0.23
0.16
0.77
0.54
0.26

G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G
G

Width
(m)
0.04
0.07
0.02
0.02
0.16
0.19
0.03
0.05
0.05
0.06
0.07
0.06
0.06
0.07
0.08
0.07
0.10
0.19

2.53 G
1.97 G
1.82 G
1.85 G
2.70 G
2.85 G
1.52 G
1.80 G
1.75 G
3.02 G
4.84 G
4.58 G
6.03 G
8.19 G
9.20 G
w100
w100
w100

Flow
(m s1)
0.23
0.26
0.31
0.31
0.87
0.74
0.18
0.27
0.33
0.80
0.63
0.70
0.54
0.75
0.86

0.00 G
0.04 G
0.22 G
0.01 G
0.02 G
0.01 G
0.07 G
0.30 G
0.27 G
0.25 G
0.37 G
0.56 G
0.09 G
0.43 G
0.49 G
N/A
N/A
N/A

Discharge
(m3 s1)
0.00
0.02
0.06
0.00
0.01
0.00
0.02
0.09
0.06
0.07
0.12
0.08
0.02
0.07
0.06

0.00 G
0.02 G
0.04 G
0.00 G
0.00 G
0.01 G
0.01 G
0.05 G
0.06 G
0.07 G
0.39 G
0.50 G
0.08 G
0.53 G
1.59 G
N/A
N/A
N/A

0.00
0.01
0.01
0.01
0.00
0.01
0.00
0.02
0.02
0.01
0.17
0.13
0.01
0.07
0.29

SH = Snake Head Creek, OH = Old Hands Creek, HC = Hurdle Creek, SC = Spring Creek, RC = Reedy Creek and GD = Gold Dredge Dam.

359

R.C. Churchill et al. / Environmental Pollution 132 (2004) 355e363

3.2. Sediment

3.3. Surface water


A total of 330 surface water samples were analysed
for Hg. Very high Hg concentrations were detected in

0.12
Mercury (mg 1-1)

A total of 316 sediment samples were analysed for Hg.


Mercury was found within the sediment prole in Hurdle,
Spring and Reedy Creeks with concentrations varying
with depth (Fig. 2). Mercury concentrations in Snake
Head and Old Hands Creeks and Gold Dredge Dam were
below the lower detection limits of ICP-OES analysis.
The Hg concentration was signicantly dierent between creeks and between sediment depths within any
one creek. Hurdle, Spring and Reedy Creeks had signicantly higher Hg concentrations in the sediment
prole compared with the control creeks (Snake Head
and Old Hands) and Gold Dredge Dam (F5;297 18:86,
p ! 0:001). For creeks combined, there was a slight
two-way interaction between creek and depth for Hg
concentration (F9;297 1:93, p 0:047). This suggested
that the Hg concentration varied in the sediment prole
dierently in each creek. For those creeks in which Hg
was detected, higher concentrations were found in the
top sediment layer.
Further analysis of Reedy Creek was completed to
determine if any dierence could be detected for Hg
concentrations between individual sites along Reedy
Creek and the depth in the sediment prole. The Hg
concentration steadily increased in the sediments from
site 1 to site 4 before declining to below detection at sites
8 and 9 (F8;117 29:25, p ! 0:001; Fig. 3).

Sampling
trip

0.08

May

0.04

June
0.00

August
SH

OH

HC
SC
Creek

RC

GD

Fig. 3. The mean Hg concentration (mg kg1) G1 S.E. in the sediment


prole (top = 0e5 cm, middle = 10e30 cm and bottom = 40e60 cm)
for each of the nine sites along the length of Reedy Creek, northeast
Victoria, Australia.

the surface waters for all creeks, except Old Hands


(Fig. 4). There was a two-way interaction between creek
and trip (F10;312 37:40, p ! 0:001). This suggested that
the Hg concentration in the surface waters varied over
time dierently for each creek. The Hg concentration
was generally higher in June than the previous month
and in August it dropped below the lower detection
limits of ICP-OES analysis at all creeks (F2;327 295:63,
p ! 0:001). Spring Creek did not follow this pattern; Hg
concentrations were similar in June and May. The
highest Hg concentrations in the surface waters were
detected from Hurdle and Reedy Creeks and Gold
Dredge Dam in June (F5;324 9:28, p ! 0:001; Fig. 4).

0.07
0.12

0.05
0.04

Sediment
profile

0.03
Top

0.02
0.01

Middle

0.00

Bottom
1

5
Site

7
1

Fig. 2. The mean Hg concentration (mg kg ) G1 S.E. in the sediment


prole (top = 0e5 cm, middle = 10e30 cm and bottom = 40e60 cm)
for each creek studied in the Reedy Creek sub-catchment, northeast
Victoria, Australia (SH = Snake Head Creek, OH = Old Hands
Creek, HC = Hurdle Creek, SC = Spring Creek, RC = Reedy Creek
and GD = Gold Dredge Dam).

Mercury (mg l-1)

Mercury (mg kg-1)

0.06

Sampling
trip

0.08

May

0.04

June
0.00

August
SH

OH

HC
SC
Creek

RC

GD

Fig. 4. The mean Hg concentration (mg l 1) G1 S.E. in the surface


waters during each sampling trip (May = rst ow, June = ood
event and August = high ow) for each creek studied in the Reedy
Creek sub-catchment, northeast Victoria, Australia (SH = Snake
Head Creek, OH = Old Hands Creek, HC = Hurdle Creek,
SC = Spring Creek, RC = Reedy Creek and GD = Gold Dredge
Dam).

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R.C. Churchill et al. / Environmental Pollution 132 (2004) 355e363

Individual sites in Reedy Creek were examined to


determine if any dierence could be found among sites
along Reedy Creek during each sampling trip (Fig. 5).
The general temporal pattern for Hg concentrations
at all sites began at a mid range in May, increased in
June then decreased to a concentration that was below
detection limits in August. Again, there was a signicant
two-way interaction between site along Reedy Creek
and the trip (F16;135 5:50, p ! 0:001) and it was
revealed that seasonal trends in Hg concentration were
not the same at all sites along Reedy Creek.
3.4. Sedimentesurface water
For all creeks the Hg concentration in the surface
waters was correlated with the Hg concentration in the
sediment (Pearsons r2 0:35, p ! 0:05). The mercury
concentration in the surface waters was always higher
than the mercury concentration in the sediments
(t52 10:82, p ! 0:001).

4. Discussion
Some aspects of the physico-chemical variability
within watercourses enhance the mobilisation of heavy
metals (Reuther, 1992) and the transformations of the
dierent oxidation states (Andersson, 1979). Variability
in the pH, temperature, dissolved oxygen, conductivity
and discharge has been shown to play a role in the
mobilisation and transformation of heavy metals (Benes
and Havlik, 1979; Reuther, 1992). Transformations can
also be biologically induced by micro-organisms that rely
on the physico-chemical interactions of the watercourse
and sediment for stimulation (Nagy and Olson, 1980).
Although the signicance of the physico-chemistry of the

Mercury (mg 1-1)

0.12

Sampling
trip

0.08

May

0.04

June
0.00

August
1

5 6
Site

Fig. 5. The mean Hg concentration (mg l1) G1 S.E. in the surface


waters during each sampling trip (May = rst ow, June = ood
event and August = high ow) for each of the nine sites along the
length of Reddy creek, northeast Victoria, Australia.

water bodies has been reported extensively with reference


to heavy metals in the aquatic environment (Benes and
Havlik, 1979; Nagy and Olson, 1980; Winfrey and Rudd,
1990; Miskimmin et al., 1992; Reuther, 1992; Tremblay
and Lucotte, 1996; Plourde et al., 1997) there are few
supporting eld data citing a direct relationship.
Thorp and Lake (1973) reported slight decreases in
the pH (mean decrease = 0.4) over the sampling period
(six months) of six sites in the South Esk River,
Tasmania. However, in the Reedy Creek sub-catchment,
the physico-chemical data did not indicate any particular variability in the conditions of the surface waters.
This suggested that there was no signicant dierence in
the physico-chemistry of the control creeks (Snake Head
and Old Hands) compared with the impacted creeks
(Hurdle, Spring and Reedy Creeks and Gold Dredge
Dam). There was a seasonal eect caused by the higher
discharge rate in June after the rst ood event from
winter rain. The physico-chemical results for Spring and
Reedy Creeks stood out particularly, as they had the
highest discharge rates, coldest temperatures and highest
dissolved oxygen content, compared to all the other
creeks studied over the sampling period. The variability
of the physico-chemical conditions within these two
creeks may have been enough to stimulate physical,
chemical and/or biological reactions within the sedimentesurface water interface (Winfrey and Rudd,
1990; Miskimmin et al., 1992; Tremblay and Lucotte,
1996; Plourde et al., 1997).
The concentrations of Hg detected in the bed sediments of Hurdle, Spring and Reedy Creeks were within
the worldwide range of naturally occurring background
concentrations reported by Jones and Jarvis (1981).
However, there was some spatial variability in the Hg
concentrations along Reedy Creek within sites that were
above these natural background levels. The Hg concentration in the sediments of Reedy Creek increased from
site 1 to site 4 (upstream) then decreased to site 7
(midstream) before becoming undetectable at sites 8 and
9 (downstream). At sites 3, 4 and 5 the Hg concentrations were above naturally occurring background
levels that could be due to the location of the sites. All
three sites had large depositional zones and it has been
suggested that heavy metals settle from the water
column into the sediments and remain there for
a number of years (Tiller, 1989). Wayne et al. (1996)
detected abnormally high concentrations of Hg in
depositional sediments of the Carson River, Nevada,
downstream of mining sites 106 years after the cessation
of works.
In polluted stream sediments it has been shown that
the highest heavy metal concentrations are associated
with organic matter (humic and uvic acids and
colloids) and ne-grained sediment fraction (clay, silt
and ne sand) (Duzzin et al., 1988; Meili et al., 1991;
Tremblay and Lucotte, 1996; Wayne et al., 1996). The

R.C. Churchill et al. / Environmental Pollution 132 (2004) 355e363

Environment Protection Authority (1984) and Duzzin


et al. (1988) recorded that heavy metals have a higher
anity for ner sediment particles such as silt, organics
and sand which are usually found on the very surface of
the sediment bed. Gibbert et al. (1994) and Grondin
et al. (1995) also found that this occurred in the bed
sediments of the Rhone River and wetland soils in
Quebec, respectively. The results from the Reedy Creek
sub-catchment were consistent with these reports as Hg
concentrations did vary with depth in the sediment prole. In the creeks where Hg was detected the concentrations were highest in the top samples (0e5 cm) and
decreased with depth of the sediment prole.
To determine the location of heavy metals within the
dierent sized sediment particles, the Environment
Protection Authority (1984) separated samples by
sieving into two groups: !63 mm and 63 mme2 mm.
Their data suggested there were signicantly higher
concentrations of heavy metals in the !63 mm fraction
that demonstrated a strong association between heavy
metals and the smaller sized sediment particles. The
sediment samples in this project were sieved to !2 mm,
which is termed a whole sample by the Environmental
Protection Authority (D. Tiller, Environmental Protection Authority Victoria, pers. comm.) because it only
removed the larger debris and gravel. A 2 mm sieve was
used as this was the common soil fractioning method at
the Agriculture Victoria laboratory where the samples
were analysed. Had the samples been sieved to !63 mm,
the heavy metal concentrations detected in the sediments
in the Reedy Creek sub-catchment may have been
considerably higher.
The usefulness of measuring heavy metal concentrations in surface waters as a reliable indication of
contamination has been questioned due to the high
uctuation of heavy metals in surface waters (Bycroft
et al., 1982). This study also detected a high uctuation
of Hg in the surface waters of the Reedy Creek subcatchment.
The concentrations of Hg in the surface waters were
higher in each creek in the Reedy Creek sub-catchment
compared with the naturally occurring background
levels reported by Beaton (1998). However, Hart (1982)
noted that the east coast of Australia is in a mercuriferous
zone and that higher background levels of Hg may be
found in the rivers draining this area. The concentrations
of heavy metals detected revealed that the Reedy Creek
sub-catchment (including the control creeks) was contaminated by heavy metals to some degree. Although,
these concentrations were high (up to 0.11 mg l 1), they
are not unusual for rivers in northeast Victoria subjected
to gold mining. Tiller (1990) recorded Hg concentrations
of 0.1 mg l 1 in the Ovens River at Peechelba and Bright
approximately 45 km away. Bycroft et al. (1982) found
that Hg concentrations in the Lerderderg River were also
higher than naturally occurring background levels, but

361

a trend could not be inferred from their data due to a


high uctuation of Hg concentration within any one site.
A temporal trend of Hg concentrations in the surface
waters could be inferred for the Reedy Creek subcatchment. The Hg concentrations in each creek were
above background levels in May when the rst water
ow occurred in most of the creeks. After the rst ood
event in June, heavy metal concentrations increased to
their highest concentration detected during this study.
However, the heavy metal concentrations were below
detection limits for each creek in August following sustained high ows throughout June and July. Thorp and
Lake (1973) detected a pulse of cadmium and zinc in
the South Esk River, Tasmania after ooding and
Duzzin et al. (1988) found that ooding caused worse
contamination due to the mobilisation of the negrained sediments. The particulate matter and adsorbed
Hg sink to the creek bed and are more easily resuspended during a storm event or periods of ood (Parks
et al., 1986; Meili et al., 1991).
Initial high concentrations of Hg recorded in May
could be due to physico-chemical variability of temperature, pH, conductivity and dissolved oxygen content
resulting in an increase in heavy metal concentrations, as
found by Rudd and Turner (1983), Parks et al. (1986)
and Meili et al. (1991). During the rst ush of water in
June the highest concentrations of Hg were probably
caused by the physical mobilisation of ne-grained
sediments. The return to background concentrations in
August, even though discharges were still high, may be
due to a dilution eect or a reduction of the ne surcial
particulates from the creek beds (Environment Protection Authority, 1984; Duzzin et al., 1988).
In this study, examination of Hg concentrations in
the surface water among individual sites in Reedy Creek
did not show the same spatial pattern as found in the Hg
concentrations in the sediment. Although the Hg concentration in the surface water of Reedy Creek collectively followed a temporal pattern, the individual sites
all had relatively similar Hg concentrations. Therefore,
it can be assumed that the Hg concentration in the surface water was being pulsed down the length of Reedy
Creek in detectable concentrations in May and June and
possibly entering the Ovens River. This may explain the
high Hg concentrations detected by Tiller (1990) at
Peechelba, a town on the Ovens River. Similar movement of Hg was reported for the Upper Goulburn River
system, with Hg concentrations detected down the
lengths of the Goulburn River, Morning Star Creek
and Raspberry Creek, Victoria (Environment Protection
Authority, 1984).
From the surface water data, the Reedy Creek
sub-catchment (including the control creeks) appeared
to have some degree of heavy metal enrichment from past
gold mining activities. The revised Australian and New
Zealand Environment and Conservation Council water

362

R.C. Churchill et al. / Environmental Pollution 132 (2004) 355e363

quality guidelines (ANZECC, 2000b) and the Australian


drinking water guidelines (National Health and Medical
Research Council (NHMRC), 1996) established guidelines for the protection of aquatic ecosystems (Hgd
0.00013 mg l 1), irrigation water quality (Hgd0.03 mg
l 1) and drinking water quality (Hgd0.001 mg l 1).
During May and June the Hg concentrations in the
surface waters of each creek studied in the Reedy Creek
sub-catchment (including the control creeks) were all
above the guidelines for each water use.
Most heavy metals have a high anity for the sediments, which usually results in higher concentrations in
the sediments than in the surface waters (Parkman and
Meili, 1993). Kudo et al. (1975) found as much as 97%
of the total Hg in a stream was located in the sediments
because of the high attraction of heavy metals for the
sediments. However, the data from this study showed
quite the opposite. There were higher concentrations of
heavy metals detected in the surface waters than for the
sediments by almost an order of magnitude.
The low detection of Hg in the sediment prole could
be due to several factors. It was unlikely that the heavy
metals were uniformly distributed throughout the creek
sediments. Therefore, the random sampling method of
this study may have underestimated the Hg concentrations in the sediment prole. Furthermore, whilst
mining for gold in the 1850s, Reedy Creek was diverted
from its original course to its current bed. Therefore,
a large amount of the Hg may have settled out in the old
creek bed, which was not sampled in this study. Also,
Spring and Reedy Creeks consist of a bed of cobbles and
gravel, therefore organic matter and other ne particulates which provide the necessary binding sites for
heavy metals may only be found in depositional zones
(Environmental Protection Authority, 1984; Duzzin
et al., 1988; Meili et al., 1991). Both the sediment and
surface water data at sites 3, 4 and 5 (Woolshed Falls
and below) along Reedy Creek showed higher concentrations of Hg in the depositional zones.
The high concentration of Hg detected in the surface
waters could also be due to several factors. The rst ow
after summer that occurred in May possibly stimulated
physical, chemical and/or biological mobilisation and
transformation of the heavy metals. With the June ood
event the Hg may have been washed in from the ood
plain and bank erosion (Hakonson et al., 1980; Wayne
et al., 1996), thereby increasing the concentration of Hg
detected in this study. Parks et al. (1986) found that the
resuspension of unconsolidated sediments is important
to the Hg budget in freshwater streams and may cause
transient increases in the total Hg content in surface
waters during and after ooding events. After more
winter rainfall and runo the creeks were at high ow
and a subsequent dilution eect from the increased
discharge rates may have prevented the detection of Hg
in August.

5. Conclusions
Mercury is still prevalent in the water and surface
sediments of streams in the Reedy Creek sub-catchment
in northeast Victoria more than 100 years after the
cessation of gold mining. In the surface sediments the
concentrations of Hg are highest at the end of summer
following a period of drying and pool recession that
occurs in intermittent streams in Australia. This may be
due to accumulation of ne sediments and organic
matter that are then mobilised during ood ow causing
a pulse of elevated concentrations of Hg in the water
column as observed during the high ows in winter.
During the rst ood event the concentrations of Hg
exceeded the Australian water quality guidelines and
highlights to local water authorities the importance of
runo events when assessing the quality and toxicity of
water supplies.

Acknowledgements
We are grateful to Dr. Bill Slattery and Glenn
McDonald from the Agriculture Victoria laboratory at
Rutherglen for the use of equipment and co-supervision
of the project. Thanks also to the Wooragee Landcare
Group (especially Glen Scholeld). The Department of
Environmental Management and Ecology at La Trobe
University provided nancial assistance.

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