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Baseline
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Pattimura University, Ambon, Indonesia
Marine Ecology Research Centre, School of Environment, Science and Engineering, Southern Cross University, Lismore, NSW, Australia
Environmental Analysis Laboratory, Southern Cross University, Lismore, NSW, Australia
d
Department of Fisheries and Marine Science, Pattimura University, Ambon, Indonesia
b
c
a r t i c l e
i n f o
Keywords:
Mercury
Sediment
Sequential extraction
Buru Island
Gold mining
a b s t r a c t
In November 2011 gold was found at Mount Botak, Buru Island, Mollucas Province, Indonesia. Since 2012
mercury has been used to extract the gold requiring large volumes of water and resulting in deposition of
mercury into Wamsait River and Kayeli Bay. Total mercury in waste ponds was over 680 mg/kg. In sediments at the mouth of the local river and a small feeder creek >3.00 mg/kg and >7.66 mg/kg respectively.
River and bay sediments were proportionately higher in available mercury than elemental mercury and
more strongly bound mercuric sulde compared to that in trommel waste. This preliminary investigation
raises concerns about the long term distribution and speciation of mercury. The oodplain is an important agricultural resource, and Mollucas Province is recognised nationally as the centre for Indonesian
sh stocks. Challenges for management include communicating the potential future risks to the community and leaders and identifying mechanisms to reduce mercury waste.
Crown Copyright 2013 Published by Elsevier Ltd. All rights reserved.
0025-326X/$ - see front matter Crown Copyright 2013 Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.marpolbul.2013.09.011
Island approved the research activity and access to the mine site
was gained through the exisiting security network. The sampling
focus was in the Mount Botak area and associated trommel activities near Wamsait River (Fig. 1). Ore and trommel waste samples
were collected on site, sediment samples were collected by hand
in river areas at road crossing and by snorkel at the marine sites.
All samples were stored in polyethylene zip lock bags and where
possible the sediment samples were stored on ice prior to freezing
at Pattimura University laboratories in Ambon. Approximately
5.0 g of homogenised sample from each site was dried at room
temperature and sent to Southern Cross University for analyses.
For quarantine purposes and prior to use, all samples were sterilised by Gamma irradiation at 50 kGy. Gamma rays are short wavelength electromagnetic radiation and this sterilisation method is
known as a cold process due to the low level of temperature
change. This sterilization method is a more suitable for maintaining mercury concentrations, speciation and sample integrity compared with the alternative of autoclaving or chemical treatment
(Yu and Yan, 2003).
Two acid extraction techniques were used in microwave assisted digestion for comparative assessment. Sediment were dried
for 48 h at 40 C, homogenised, and ground with acid cleaned and
distilled water rinsed mortar and pestles. From each homogenate
duplicate 0.2 0.01 g samples were weighed into separate Teon
tubes. Digestions were completed using 69% Aristar HNO3 and a
second set of digestions were completed using an aqua regia 1:3
concentrated HNO3:HCl. Samples were microwaved for 20 min
using a microwave accelerated rection system (MARSXpress)
with 1600 W IEC and frequency of 2450 MHz and allowed to cool
for 15 min before decanting. The elemental analysis was conducted
using a Perkin Elmer NexION 300D Inductively Coupled Plasma
429
Mass Spectrometer (ICPMS). Optimisation was performed as outlined in the NexION 300D users manual, in particular, the nebuliser gas ow rate and torch alignment were adjusted to yield the
greatest sensitivity possible while maintaining low levels of oxides
(<2%) and doubly-charged ions (<3%). Once optimisation was completed, appropriate calibration standards were measured. A threepoint calibration curve of 1, 5 and 20 lg/L Hg and 0.1, 1.0 and
10.0 lg/L Au were prepared to generate a calibration coefcient
of 0.9999 or greater. The sample solutions were then analysed
against this calibration curve to determine the concentrations. A
calibration standard and independent soil digests were analysed
at regular intervals during analytical runs to ensure the instrument
maintained acceptable linearity and sensitivity criteria.
Duplicate blanks, Montana 2711a certied reference material,
and the Australian National Measurement Institute reference sediment, AGAL-12, were digested and analysed with each batch of
samples. The recovery rates for mercury are shown in Table 1.
The mercury recovery rates from the certied reference materials
showed reasonable recovery rates between the two extraction
techniques with aqua regia slightly over-estimating mercury concentrations. The % recovery of mercury from both reference materials were within 10% of the actual certied value after nitric acid
digestion.
The procedure for the sequential extraction of mercury described in Bloom et al. (2003) and Yu et al. (2012) was used in this
study. Table 2 explains the process used for all samples from the
study area along with blanks and the two certied standards. For
the purposes of method verication the sum of the sequential
extraction steps F1 to F5 were compared with the results from
the extractions of total recoverable mercury. The sum of the
sequential extraction showed good mercury recoveries from the
Fig. 1. Location map of Buru Island, Gunung Botak (Mount Botak) mine site, and sampling areas. The second and more recently developed (late 2012) Gogrea mine site, while
not part of this study, is also shown.
430
Table 1
Results of analyses of two standard reference materials and the relative % recovery.
Sample
Montana
2711a
% Recovery
AGAL-12
% Recovery
7.420
8.110 0.750
8.401 0.475
6.700 0.151
0.530
106
0.53 0.057
100
113
0.617 0.175
116
90
0.399 0.070
75
Table 2
Extraction process used for the 5 step sequential extraction and the operational description (Bloom et al. (2003) and Yu et al. (2012)).
Sequential
step
Operational
discription
Preparation
F1
Water soluble
F2
Sample dried at 40 C and ground with motar and pestle and 0.2 0.01 g weighed
Weighed sample mixed with 20 mL Milli-Q water, shaken at room temperature for 18 h, centrifuged at 3000 rpm for 20 min, extract
decanted into acid clean glass vials with Teon caps, repeated 3 and all washes combined with extract and preserved with 0.2 N BrCl
for analyses
Sample from F1 mixed with 20 mL 0.1 M CH3COOH and 0.01 M HCl, shaking, washing, and sample preservation as above
F3
Sample from F2 mixed with 20 mL 1 M KOH, shaking, washing, and sample preservation as above
F4
F5
Sample from F3 mixed with 20 mL 12 M HNO3 shaking, washing, and sample preservation as above
Sample from F4 microwave digested for 30 min in aqua regia 1:3 concentrated HCl:HNO3
Stomach acid
soluble
Organochelated
Elemental Hg
Mercuric
sulde
Table 3
Mean mercury concentrations (mg/kg) and standard deviations from sequential extractions and total digests of duplicate ore, trommel waste, and sediment samples, Buru Island,
Indonesia. Mean gold concentrations (mg/kg) are also provided for the total extractable aqua regia digest for some samples. Refer to Table 2 for F1F5 extraction proceedures.
Sample type
Sediments
Ore and waste material
Unprocessed ore (low
grade)
Unprocessed ore (high
grade)
Ponded trommel waste after
rst gold extraction
Semi processed ore
Waste pond storage 1
current site (mid 2012)
Final processing waste pond
storage 2 past site (early
2012)
Final processing waste pond
storage 3 early site
(2011)
Sediment from feeder creek
to main creek
Tributary to Wamsait River
(near bridge)
Wamsait Estuary
20 m offshore Wamsait
River
10 m offshore from Kayeli
Beach Village
20 m offshore from Kayeli
Beach Village
Total extractable
Hg/HNO3
F1
F2
F3
F4
F5
Total
14.25 (6.46)
80.72 (2.00)
0.695 (0.29)
19.63 (0.94)
9.278 (1.97)
0.247 (0.07)
27.2 (32.3)
0.741 (0.35)
6.783 (1.83)
0.693 (0.01)
10.45 (2.60)
72.66 (1.16)
7.61 (1.49)
Total extractable
aqua regia
Hg
Au
7.38 (0.79)
7.78 (3.23)
2.23 (0.63)
10.1 (0.66)
10.4 (0.82)
1383 (78)
691 (12)
807
825 (57)
918 (24)
166 (23)
22.41 (21.8)
1.830 (0.06)
303 (247)
7.224 (0.12)
369
10.7
630 (2.1)
10.3 (0.8)
632 (62)
11.89 (0.28)
131 (2.0)
47.9 (3.2)
3.64 (3.05)
31.55 (6.11)
604 (7.3)
723
838 (115)
870 (22)
159 (12)
12.74 (5.09)
4.426 (0.36)
13.08 (3.05)
614 (9.3)
652
789 (65.1)
682 (6.3)
187.0 (4.1)
0.890 (0.15)
0.148 (0.07)
0.198 (0.00)
0.741 (0.06)
5.336 (0.30)
7.31
7.66 (0.42)
9.28 (0.58)
9.03 (6.25)
0.099 (0.00)
0.05 (0.07)
0.199 (0.00)
0.149 (0.07)
0.199 (0.07)
0.696
0.63 (0.13)
1.827 (0.83)
0.095 (0.02)
0.099 (0.00)
0.148 (0.07)
0.099 (0.14)
0.443 (0.35)
0.148 (0.07)
0.398 (0.40)
0.148 (0.07)
0.642 (0.07)
0.074 (0.11)
1.061 (0.17)
0.568
2.992
0.64 (0.37)
2.35 (0.28)
0.548 (0.08)
3.564 (0.43)
1.18 (0.07)
0.99 (0.45)
0.05 (0.07)
N/D
0.099 (0.20)
0.099 (0.00)
0.418 (0.38)
0.666
0.4 (0.01)
0.783 (0.10)
N/D
0.05 (0.07)
0 (0.00)
0.198 (0.00)
0.099 (0.00)
0.05 (0.07)
0.397
0.35 (0.00)
1.17 5(0.10)
0.37 (0.17)
431
Fig. 2. Mercury concentrations (mg/kg) in river and marine sediments during the current study.
432
Fig. 3. The relative contribution of each sequential extraction phase to the total mercury in ore and sediment samples. Extraction phases F1F5 are explained in Table 2.
Acknowledgements
This research was supported by the federally funded Indonesian
SAME Program and the Marine Ecology Research Centre, School of
Environment, Science and Engineering, and Environmental Analysis Laboratory at Southern Cross University. Special thanks to Barbara Harrison and Jenny Nolan for laboratory support and Greg
Luker for GIS support. Quarantine Permit No: IP12022133.
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