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Marine Pollution Bulletin 73 (2013) 306–313

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Marine Pollution Bulletin


journal homepage: www.elsevier.com/locate/marpolbul

Trace metals associated with deep-sea tailings placement at the Batu Hijau
copper–gold mine, Sumbawa, Indonesia
Brad M. Angel a,⇑, Stuart L. Simpson a, Chad V. Jarolimek a, Rob Jung a, Jorina Waworuntu b,
Grant Batterham b
a
Centre for Environmental Contaminants Research, CSIRO Land and Water, Locked Mailbag 2007, Kirrawee, NSW 2232, Australia
b
PT Newmont Nusa Tenggara, Batu Hijau Project, Sumbawa Barat, Nusa Tenggara Barat, Indonesia

a r t i c l e i n f o a b s t r a c t

Keywords: The Batu Hijau copper–gold mine on the island of Sumbawa, Indonesia operates a deep-sea tailings place-
Copper ment (DSTP) facility to dispose of the tailings within the offshore Senunu Canyon. The concentrations of
Arsenic trace metals in tailings, waters, and sediments from locations in the vicinity of the DSTP were determined
Mercury during surveys in 2004 and 2009. In coastal and deep seawater samples from Alas Strait and the South
Deep sea tailings placement
Coast of Sumbawa, the dissolved concentrations of Ag, As, Cd, Cr, Hg, Pb and Zn were in the sub lg/L
range. Dissolved copper concentrations ranged from 0.05 to 0.65 lg/L for all depths at these sites. Dis-
solved copper concentrations were the highest in the bottom-water from within the tailings plume inside
Senunu Canyon, with up to 6.5 lg Cu/L measured in close proximity to the tailings discharge. In general,
the concentrations of dissolved and particulate metals were similar in 2004 and 2009.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction Table S1). The existing DSTP facilities of PTNNT deposit tailings
at depths of between 1000 and 3000 m, which are considerably
The Batu Hijau copper–gold mine is located on the southwest deeper than a number of past marine disposal operations that
corner of the island of Sumbawa in the province of West Nusa have deposited at depths of between 80 and 500 m (e.g. Island
Tenggara, Indonesia (Fig. 1). The mine is operated by PT Newmont Copper, Kitsault – Canada; Atlas Copper – Philippines; Black An-
Nusa Tenggara (PTNNT) and processes ore at a rate of approxi- gel – Greenland; Minahasa Raya – Indonesia). The justification
mately 130,000 t/d. The open-pit mine is at an elevation of for selecting DSTP for tailings management is usually based on
450 m above sea level. Crushed ore is processed through a grinding the challenges in maintaining on-land tailings storage facilities
circuit and flotation-based concentrator for copper and gold in high rainfall, mountainous and seismically active terrain and
extraction. The tailings slurry from the operation consists of finely the proximity to deep oceanic canyons. The DSTPs are engineered
ground rock that is disposed of by a deep-sea tailings placement to ensure that tailings density, seabed gradients and oceano-
(DSTP) facility. This method of disposal was determined to have graphic currents and upwelling characteristics at the pipeline exit
several advantages over on-land disposal and was approved by point minimise material rising into the surface waters. The Batu
the Government of Indonesia (ANDAL, 1996). The tailings, which Hijau copper/gold mine is one of the larger examples of DSTP in
typically comprise approximately 60% solids, are conveyed by the world and deposits tailings at the greatest depth.
gravity in a pipeline from the process plant to the outfall discharge The discharged tailings slurry contains elevated concentra-
point at the head of a steep submarine canyon (the Senunu Can- tions of a range of metals that have the potential to impact on
yon) located 3.2 km off shore at 110 m depth. From the point of the marine environment. However, the dilution in the receiving
discharge, the tailings, flow down the steep off-shore canyon as a environment is predicted to result in concentrations being below
bottom-attached density current and are ultimately deposited in those predicted to cause effects to aquatic biota (ANZECC/ARM-
the deep oceans at depths in excess of 3000 m. CANZ, 2000). The present study investigated the water-borne
The use of DSTP for mining operations is not uncommon in and benthic sediment metal concentrations in Senunu Canyon,
Indo-Pacific archipelagic nations, and has also been used by the South Coast of Sumbawa Island, and Alas Strait, which sepa-
mines in the northern hemisphere (Apte and Kwong, 2004; Jones rates Sumbawa and Lombok Islands. Depth profile sampling was
and Ellis 1995; Poling et al., 2002; SAMS, 2010) (Supplementary performed at a range of locations to allow comparison of dis-
solved metals near the discharge point with those in the sur-
⇑ Corresponding author. Tel.: +61 297106851; fax: +61 297106800. rounding environment and with internationally accepted water
E-mail address: brad.angel@csiro.au (B.M. Angel). quality guidelines.

0025-326X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.marpolbul.2013.04.013
B.M. Angel et al. / Marine Pollution Bulletin 73 (2013) 306–313 307

Fig. 1. Location of the sampling sites in the water off Sumbawa Island, Indonesia.

2. Methods soaking in 50% analytical grade (AR) nitric acid for 48 h, and then
soaking in 10% ultra-pure grade hydrochloric acid (Merck Trace-
2.1. Field site pur) for at least 72 h, and then soaked in Milli-Q water for at least
48 h, with at least five rinses with Milli-Q water, between each
This study involved two water sampling surveys undertaken in step. Each bottle was stored inside two polyethylene sealable bags
October 2004 and April 2009 in the area shown in Fig. 1. The study for transport to and from the field.
area included five reference sites in Alas Strait, between the islands Samples were collected from between 2 and 4 depths at each
of Sumbawa and Lombok, that were sufficiently distant (20– site using acid-washed (10% HNO3 v/v) NiskinÒ samplers. The Ni-
40 km) to not be impacted by the DSTP. There were twelve sites skinÒ was suspended at the sample depths of 3, 50, and 120 m
on the south-western side of Sumbawa, within 4–8 km of the DSTP, below the surface and approximately 10 m above the sea floor
and six sites in the Senunu Canyon (sites with code ‘‘S’’) within (varied depending on site) for approximately 10 min to rinse
1.5 km of the DSTP. the sampler with sample before triggering the device to obtain
the sample. Ultratrace sampling techniques were employed in
the field similar to those described by Ahlers et al. (1990). Two
2.2. Water sample collection and treatment people were involved in the sampling operation and both wore
powderless vinyl gloves (Bioclean 100, Nitritex Ltd). One person
High purity deionised water (18 MX/cm, Milli-Q, Millipore) was operated the Niskin sampler by releasing the pressure valve and
used in all equipment washing procedures and for the preparation releasing the tap to dispense the sample. The second person han-
of metal standards. One-litre low-density polyethylene (LDPE) dled the LDPE and FEP bottles, which involved removing bottles
(Nalgene) bottles were used for sampling waters for all metals from zip-lock bags, removing the lids and filling with the sample
other than mercury and 1-L fluorinated ethylene propylene (FEP) that was dispensed from the Niskin sampler, closing the lid, and
(Nalgene) bottles were used for sampling waters for mercury anal- replacing the bottle back into two zip-lock bags. For purposes
yses. The LDPE bottles were cleaned rigorously before use, using a of quality assurance/quality control (QA/QC) during sampling of
three-stage sequential washing procedure. This involved soaking waters, at least 10% site duplicates and 10% field blanks (air
bottles and caps in 2% detergent solution (Extran) for at least 2 h, blanks) were collected.
then soaking in 10% HNO3 (Merck, Analytical Reagent grade) for Following collection, samples were stored in ice-filled cooler
at least 24 h, and then soaking in 1% high purity nitric acid (Merck boxes until return to the laboratory. The samples were then filtered
Tracepur) for at least 48 h, with at least five rinses with Milli-Q (Angel et al., 2010a; Hatje et al., 2003) within 8 h of collection
water between each step. The 1-L FEP bottles were cleaned by using acid-washed (10% HNO3, Tracepur, 24 h) polycarbonate filter
308 B.M. Angel et al. / Marine Pollution Bulletin 73 (2013) 306–313

rigs (Sartorius) fitted with membrane filters (50 mm, type HA, Mil- organic mercury present to inorganic mercury. After at least
lipore). Filtrates were transferred into 1 L LDPE and FEP bottles 90 min a 50 lL volume of hydroxylamine solution (3 M) was added
(Nalgene) following a rinse with the initial filtrate. The filtrates to destroy any residual BrCl. The vessel was connected to a custom-
were preserved by addition of 2 mL/L concentrated HNO3 (Merck built purge trap system and 0.5 mL stannous chloride solution
Tracepur). (20% m/V) was added to reduce the inorganic mercury to elemental
mercury. The elemental mercury was purged from solution in a
2.3. Physicochemical measurements nitrogen stream (20 min purge time) and trapped on a gold-coated
sand trap. The trap was transferred to a thermal desorption unit
A CTD probe (STD-12 Plus profiler with dissolved oxygen (DO) interfaced to a Brooks Rand AFS. The trap was connected to a mer-
sensor and transmissometer) was deployed at every water sam- cury-free helium gas stream and rapidly heated to 320 °C. The re-
pling site and measurements of water density, light transmission, leased mercury was quantified by the AFS.
dissolved oxygen, salinity, and temperature profiles were under- As part of QA/QC for each method, 10% of samples had spike
taken prior to sample collection. recoveries and analytical duplicates determined, and at least one
certified reference seawater was analysed per batch of samples.
2.4. Chemical analyses The certified reference seawaters included CASS-4 obtained from
the National Research Council Canada and BCR-579 obtained from
The total dissolved arsenic concentrations were determined by the Institute for Reference Materials and Measurements at the
hydride-generation atomic absorption spectrometry (AAS), using European Commission Joint Research Centre.
procedures based on the standard methods described by APHA
(2012). Samples were first digested by addition of potassium per-
3. Results and discussion
sulfate (1% m/v final concentration) and heating to 120 °C for
30 min in an autoclave followed by the addition of concentrated
3.1. Water quality
hydrochloric (3 M final concentration). Arsenic (V) was then re-
duced to arsenic (III) by addition of potassium iodide (1% m/v final
Dissolved oxygen was 5.7–6.5 mg/L at the surface for all sites
concentration) and ascorbic acid (0.2% m/v final concentration)
during the 2004 and 2009 studies and decreased with depth to less
and left standing for at least 30 min at room temperature. Arsenic
than 2 mg/L in the depths of Senunu Canyon. Surface temperatures
concentrations were then measured by hydride-generation AAS
were between 25 and 27 °C during the 2004 study and between 28
operating under standard conditions recommended by the manu-
and 30 °C during the 2009 study. The thermocline in each study
facturer (Varian VGA). Arsenic (III) in solution was reduced to ar-
was measured between 20 and 200 m depth in the Senunu Canyon,
sine by borohydride, which was stripped with nitrogen gas into a
with temperatures decreasing to less than 10 °C at 300–400 m depth
silica tube and electrically heated at 925 °C. Heating converted ar-
and reported to be 1–2 °C at depths of 2000–4000 m (LIPI, 2004).
sine into arsenic vapour whose atomic adsorption was measured.
Thermoclines were detected at depths between 75–100 and 130–
Dissolved cadmium, copper, lead, and zinc were analysed using
140 m in 2004, and between 40–60 and 90–110 m in 2009.
a dithiocarbamate complexation/solvent based on a modification
From the transmissivity profiles, the tailings plume was only
of the procedure described by Magnusson and Westerlund
detected at sites within the Senunu Canyon in 2004 (S28, S15
(1981). The chelation solution combined sodium bicarbonate buf-
and S16) and 2009 (S28, S16, and CI8) studies. During the 2004
fer, ammonium pyrrolidine dithiocarbamate (APDC) and diet-
study, the top of the plume was encountered at a depth of
hyldithiocarbamic acid (DDC) complexing reagents, which were
140 m, and during the 2009 study the plume was detected at
extracted into 1,1,1-trichloroethane in place of Freon (1,1,2-tri-
approximately 190 m, both plumes being below the discharge
chlorotrifluoroethane) (Angel et al., 2010a; Apte and Gunn 1987).
depth (112 m in 2004 and 125 m in 2009). Low transmissivity
The chelation solution was cleaned before use by extracting with
values (<60%) were only detected at depths greater than 250 and
two 10 mL aliquots of 1,1,1-trichloroethane to remove any trace
220 m during the 2004 and 2009 studies, respectively, which oc-
metals remaining after rinses with deionised water. Sample vol-
curred close to the canyon floor and tailings flow from the dis-
umes (250 mL) were buffered to approximately pH 5 by addition
charge point. Light transmissivity at other South Coast and Alas
of the chelation solution, and extracted with two 10 mL portions
Strait sites showed no evidence of suspended tailings particles,
of triple-distilled trichloroethane in acid-washed (50% nitric acid,
being consistent with the southward currents through Alas Strait
48 h) Teflon separation funnels (Oak Ridge TeflonÒ FEP). The ex-
and to the south of Sumbawa Island that transport suspended par-
tracts were combined in Teflon centrifuge tubes (Oak Ridge TeflonÒ
ticles offshore (LIPI, 2004).
FEP) and the metals back-extracted into 1 mL of concentrated ni-
tric acid (Merck, Tracepur). The back extracts were diluted to a fi-
nal volume of 10 mL with Milli-Q water, and analysed by 3.2. Dissolved metal concentrations
inductively coupled plasma – mass spectrometry (ICP-MS, Agilent
7500CE) using operating conditions recommended by the manu- The QC data for the dissolved metals analyses were excellent.
facturer. The method resulted in a pre-concentration factor of The analytical detection limits achieved for the two surveys were
approximately 25 for the samples. in the range 0.04–0.1 lg As/L, 1.2–2.0 ng Cd/L, 4–10 ng Cu/L, 0.2–
The total dissolved chromium was analysed by graphite furnace 0.13 ng Hg/L, 0.3–1 lg Mn/L, 17–20 ng Pb/L, and 6–33 ng Zn/L,
AAS (Perkin Elmer, AAnalyst 600) using standard addition and which were similar to those reported for previous ultratrace metal
inductively coupled plasma atomic emission spectrometry (ICP- studies (Apte et al., 1998; Mackey et al., 2002; Angel et al., 2010a).
AES) (Varian 730 ES) was used for manganese. Matrix-matched The analytical recovery of mercury in the reference seawater BCR-
standards (QCD Analysts) were used and operating conditions rec- 579 was 101% in 2009 and for CASS-4, recoveries were between 85
ommended by the manufacturer. and 104% for As, Cd, Cu, Hg, Mn, Pb and Zn in both surveys. Spike
Total dissolved mercury was determined by cold vapour atomic recoveries were in the range 87–112%. Site and method duplicate
fluorescence spectrometry (Liang and Bloom 1993; Liang et al., coefficient of variance was generally less than 10% except for sam-
1994). A sample volume of 80 mL was dispensed into a Pyrex-glass ples with metal concentrations which were close to the analytical
purging vessel and a 0.4 mL aliquot of bromine monochloride detection limit (mean ± SD of 10 ± 9% for Cd, 11 ± 9% for Cr,
(0.2 M) in hydrochloric acid added to allow oxidation of any 17 ± 11% for Hg, 28 ± 18% for Mn, and 12 ± 9% for Zn).
B.M. Angel et al. / Marine Pollution Bulletin 73 (2013) 306–313 309

Dissolved copper concentrations were in the low or sub-lg/L with depth. However, some of the deeper samples at sites in close
range and fairly uniform in the surface water sites in the 2004 proximity to the point of discharge were much higher than the
and 2009 surveys (Supplementary Fig. 1 and Tables 1–3). The dis- afore-mentioned sites and in the low lg/L) range. In the 2004 sur-
solved copper was similar at most depths sampled in the Alas vey, the highest concentrations were 1.5, 6.5 and 4.3 lg/L mea-
Strait and South Coast zones and did not generally exhibit a trend sured in the bottom waters of sites S28, S15 and S16,

Table 1
The concentration of dissolved metals measured at sites sampled in Senunu Canyon.

Site Depth (m) Arsenic (lg/L) Cadmium (lg/L) Chromium (lg/L) Copper (lg/L) Manganese (lg/L) Mercury (ng/L) Lead (lg/L) Zinc (lg/L)
2004 2009 2004 2009 2004 2009 2004 2009 2004 2009 2004 2009 2004 2009 2004 2009
S09 3 1.20 – 0.010 – <1 – 0.11 – <1 – – – 0.06 – 0.11 –
S09 Bottom 1.15 – 0.011 – <1 – 0.09 – <1 – – – <0.02 – 0.09 –
S12 3 1.13 1.25 0.009 0.007 <1 0.1 0.07 0.10 <1 0.5 1.0 0.5 <0.02 <0.02 0.05 0.07
S12 50 1.23 1.28 0.016 0.008 <1 0.1 0.09 1.17 <1 0.7 0.4 0.9 0.02 0.63 0.14 2.61
S12 Bottom 1.22 1.50 0.028 0.019 2 0.1 0.12 0.11 <1 0.3 0.5 1.8 0.02 0.02 0.11 0.14
S15 3 1.24 – 0.013 – <1 – 0.10 – <1 – 0.4 – 0.03 – 0.20 –
S15 50 1.13 – 0.036 – <1 – 0.39 – <1 – 0.4 – 0.12 – 1.0 –
S15 Bottom 1.27 – 0.083 – 2 – 6.5 – 6 – 0.5 – 0.06 – 0.84 –
S16 3 1.28 1.30 0.013 0.006 <1 0.2 0.08 0.09 <1 1.1 0.4 1.3 0.03 <0.02 0.14 0.05
S16 50 1.34 1.43 0.031 0.01 – 0.2 0.13 0.10 <1 0.6 0.4 0.5 – 0.02 – 0.08
S16 120 – 1.62 – 0.035 <1 0.2 – 0.10 – 1.3 – 0.6 0.03 0.12 0.15 0.20
S16 Bottom 1.40 1.76 0.085 0.063 <1 0.2 4.3 4.02 3 10 0.5 0.7 0.05 0.16 0.50 1.01
S23 3 1.19 1.29 0.008 0.006 <1 0.1 0.07 0.11 <1 0.3 0.4 1.4 0.02 <0.02 0.06 0.08
S23 50 – – – – – – – – – – – – – – – –
S23 Bottom 1.12 1.43 0.010 0.009 <1 0.1 0.08 0.10 <1 <0.3 0.6 0.3 0.02 <0.02 0.05 0.08
S28 3 1.26 1.23 0.013 0.004 <1 0.1 0.11 0.10 <1 0.6 0.5 0.4 0.04 0.01 0.26 0.06
S28 50 1.31 1.32 0.034 0.007 <1 0.1 0.14 0.08 <1 0.5 0.5 0.6 <0.02 0.02 0.17 0.06
S28 120 – 1.57 – 0.032 – 0.2 – 0.12 – <0.3 – 0.4 – <0.02 – 0.14
S28 Bottom 1.42 1.66 0.059 0.051 <1 0.2 1.5 1.76 <1 3.6 0.5 0.5 0.04 0.11 0.36 0.71

Table 2
The concentration of dissolved metals measured at sites sampled in waters off the South Coast of Sumbawa Island.

Site Depth (m) Arsenic (lg/L) Cadmium (lg/L) Chromium (lg/L) Copper (lg/L) Manganese (lg/L) Mercury (ng/L) Lead (lg/L) Zinc (lg/L)
2004 2009 2004 2009 2004 2009 2004 2009 2004 2009 2004 2009 2004 2009 2004 2009
SC1 3 1.27 1.30 0.012 0.004 <1 0.1 0.07 0.08 <1 0.3 – 0.6 0.05 <0.02 0.12 0.07
SC1 50 1.38 1.40 0.031 0.010 <1 0.1 0.10 0.13 <1 0.4 – 0.6 0.04 0.03 0.17 0.42
SC1 120 – 1.65 – 0.034 – 0.2 – 0.09 – 0.5 – 1.9 – <0.02 – 0.13
SC1 Bottom 1.40 1.71 0.060 0.052 <1 0.3 0.16 0.18 <1 0.3 – 0.4 0.06 <0.02 0.35 0.23
SC2 3 1.32 1.25 0.008 0.003 <1 0.1 0.07 0.08 <1 0.4 – 1.6 0.03 <0.02 0.08 0.11
SC2 50 1.23 1.36 0.018 0.009 <1 0.2 0.08 0.09 <1 0.4 – 0.3 0.04 <0.02 0.12 0.12
SC2 Bottom 1.35 1.47 0.020 0.008 <1 0.2 0.09 0.16 1 0.5 – 1.0 0.04 <0.02 0.11 0.16
CI8 50 – 1.48 – 0.017 – 0.1 – 0.07 – 0.4 – 1.1 – <0.02 – 0.10
CI8 Bottom – 1.56 – 0.032 – 0.2 – 0.09 – 0.3 – 0.8 – <0.02 – 0.11
CI11 50 – 1.40 – 0.007 – 0.2 – 0.09 – 0.6 – 0.8 – 0.06 – 0.13
CI11 120 – 1.59 – 0.027 – 0.2 – 0.07 – 0.4 – 0.7 – 0.02 – 0.11
CO2 3 – 1.24 – 0.005 – 0.1 – 0.09 – 0.5 – 0.5 – <0.02 – 0.39
CO2 50 – 1.32 – 0.006 – 0.1 – 0.08 – 0.3 – 0.9 – 0.03 – 0.12
CO2 120 – 1.72 – 0.063 – 0.1 – 0.19 – 0.5 – 0.8 – 0.02 – 0.21
CO2 Bottom – 1.57 – 0.033 – 0.1 – 0.10 – 0.3 – 0.4 – <0.02 – 0.14
CO3 3 – 1.26 – 0.004 – 0.1 – 0.08 – 0.4 – 0.6 – <0.02 – 0.07
CO3 50 – 1.45 – 0.014 – 0.2 – 0.09 – 0.4 – 0.4 – <0.02 – 0.08
CO3 120 – 1.59 – 0.033 – 0.2 – 0.10 – <0.3 – 0.9 – <0.02 – 0.12
CO3 Bottom – 1.68 – 0.053 – 0.2 – 0.65 – 1 – 0.7 – 0.04 – 0.27

Table 3
The concentration of dissolved metals measured at sites sampled in Alas Strait.

Site Depth (m) Arsenic (lg/L) Cadmium (lg/L) Chromium (lg/L) Copper (lg/L) Manganese (lg/L) Mercury (ng/L) Lead (lg/L) Zinc (lg/L)
2004 2009 2004 2009 2004 2009 2004 2009 2004 2009 2004 2009 2004 2009 2004 2009
AS1 3 – 1.22 – 0.004 – 0.1 – 0.11 – 0.5 – 0.5 – <0.02 – 0.08
AS1 Bottom – 1.55 – 0.014 – 0.2 – 0.05 – 0.7 – 0.7 – <0.02 – 0.11
B05 3 1.23 1.26 0.007 0.005 <1 0.1 0.07 0.30 <1 0.8 – 0.4 0.02 0.09 0.06 0.31
B05 Bottom 1.11 1.38 0.010 0.008 <1 0.1 0.08 0.08 <1 0.5 – 0.5 0.03 0.02 0.10 0.06
BCM 3 1.07 1.22 0.008 0.004 <1 0.2 0.05 0.29 <1 0.5 – 1.0 0.03 0.12 0.07 0.44
BCM Bottom 1.14 1.35 0.008 0.006 <1 0.1 0.06 0.09 <1 0.7 – 0.6 <0.02 0.10 0.10 0.08
KR1 3 1.23 1.25 0.006 0.005 <1 0.1 0.05 0.26 <1 1 – 0.5 0.02 0.04 0.08 0.24
KR1 Bottom 1.26 1.45 0.011 0.011 <1 0.2 0.06 0.07 <1 0.4 – 0.4 <0.02 0.04 0.07 0.10
TJ1 3 1.23 1.61 0.005 0.025 <1 0.2 0.05 0.07 <1 <0.3 – 0.5 0.03 0.04 0.09 0.15
TJ1 Bottom 1.45 1.25 0.039 0.004 <1 0.1 0.10 0.20 <1 0.5 – 0.7 0.02 0.04 0.17 0.34
310 B.M. Angel et al. / Marine Pollution Bulletin 73 (2013) 306–313

Table 4
Dissolved trace metal concentrations in oceans and industrialised waters around the world.

Location Arsenic Cadmium Copper Mercury (lg/L) Lead (lg/L) Manganese Nickel Zinc (lg/L) References
(lg/L) (lg/L) (lg/L) (lg/L) (lg/L)
Sumbawa, Indonesia (this study)
Alas Strait 1.28 ± 0.15 0.010 ± 0.008 0.11 ± 0.08 0.0006 ± 0.0002 0.034 ± 0.032 0.54 ± 0.17 0.18 ± 0.02 0.14 ± 0.11 This study
East sumbawa 1.44 ± 0.16 0.023 ± 0.019 0.12 ± 0.12 0.0008 ± 0.0004 0.024 ± 0.017 0.46 ± 0.19 0.22 ± 0.05 0.16 ± 0.10 This study
Senunu Canyon 1.33 ± 0.16 0.025 ± 0.023 0.75 ± 1.55 0.0006 ± 0.0004 0.259 ± 0.117 1.23 ± 2.09 0.23 ± 0.08 0.33 ± 0.52 This study
Offshore and ocean waters (worldwide)
Torres straight & Gulf – <0.001– 0.036– – – – 0.94–4.60 – Apte and Day
of Papua 0.029 0.986 (1998)
Pacific ocean – 0.0003–0.11 – – – – – 0.015– Bruland et al.
0.52 (1994)
Tasman sea – 0.0025 0.03 <0.0014 0.01 – 0.18 <0.022 Apte et al. (1998)
North pacific – 0.0011 0.04 – – – 0.12 – Mackey et al.
(2002)
North atlantic – 0.0007 0.068 – 0.136 – – – Kremling and Pohl
(1989)
Southern GBRMPa – <0.0015– <0.019– – <0.01–0.12 – 0.11–0.19 <0.03– Angel et al. (2010a)
0.004 0.085 0.14
North pacific ocean – – – 0.0004 - – – – Gill and Fitzgerald
(1988)
Atlantic ocean 0.94–1.39 – – – – – – – Cutter and Cutter
(1995)
Chatham rise, pacific 1.20–1.50 – – – – – – – Ellwood and
ocean Maher (2002)
Guideline valuesb NV c
5.5 1.3 0.4 d
44 NV c
70 15 ANZECC/ARMCANZ
(2000)
a
Great barrier reef marine park.
b
ANZECC/ARMCANZ, 2000 trigger value for 95% species protection in marine waters.
c
NV = Insufficient toxicological data available for derivation of guideline trigger value.
d
Trigger value for inorganic mercury. There is insufficient toxicological data for the derivation of methyl mercury guideline trigger value.

respectively. In the 2009 survey, the highest concentrations were (Supplementary Fig. 1 and Tables 1–3). The mean concentration
1.8, 4.0, and 1.2 lg/L measured in the bottom waters of S28 and (mean ± SD) for all marine sites was 0.25 ± 0.46 lg/L, which is
S16 in the Senunu Canyon and the middle depth of S12 (site near- well below the guideline concentration of 15 lg/L applied for
est to the point of tailings discharge), respectively. These were marine waters in Australia (ANZECC/ARMCANZ, 2000). The dis-
much higher than the dissolved copper concentrations measured solved zinc did not generally exhibit a trend with depth, although
at any other sites (Tables 1–3), and are indicative of a tailings sig- some sites had higher dissolved zinc concentrations at greater
nature. The dissolved copper concentrations in the tailings liquid depth. This was most evident at deeper samples in close proxim-
ranged from 0.18 to 5.3 lg/L (Table S2) and, given the likely dilu- ity to the point of discharge, which had concentrations in the low
tion from mixing with ocean water, would indicate that some re- lg/L range. The highest concentration in 2004 was 1.0 lg/L mea-
lease of copper must be occurring from tailings particulates. sured at 50 m depth at site S15. The concentrations of dissolved
During the operation of the DSTP, the area in the vicinity of the zinc measured in 2009 at the bottom sites S28 and S16 in the Se-
turbulent tailings flow is likely devoid of most life-forms due to the nunu Canyon and the middle depth of S12 were 0.71, 1.01, and
physical impacts of the tailings. Inputs of copper to nearby seawa- 2.61 lg/L, respectively. These were much higher than any other
ter are likely to occur because of a combination of dissolved copper dissolved zinc concentrations measured, and are likely to indicate
in the tailings discharge and rapid desorption of copper from the a signature of the tailings plume. However, even the highest con-
tailings sediments as they mix with seawater. As the Senunu Can- centration measured at the middle depth (50 m) at site S12 was
yon zone adjacent to the discharge is physically impacted by the more than an order of magnitude below guideline concentrations.
tailings flow, it is not expected that many aquatic organisms would Sample sites in the Senunu Canyon and South Coast that were
reside in this zone to receive chronic impacts from dissolved met- further from the point of tailings discharge had similar zinc con-
als. Many organisms also have the ability to avoid contaminants centrations to those measured in Alas Strait, indicating that the
(Weber, 1997), and short, pulsed exposures to dissolved copper tailings plume only had a localised effect. The dissolved zinc con-
may have significantly less effect than constant chronic exposures centrations in the tailings liquid ranged from 0.08 to 0.8 lg/L
(Bearr et al., 2006; Angel et al., 2010b). While the dissolved copper (Table S2) and were lower than or similar to some samples close
concentrations were below the Indonesian receiving water stan- to the tailings discharge, indicating zinc is released from the tail-
dard for the protection of marine life (8 lg/L; Kepmen LH 51/ ings particulates.
2004) at all sites, the concentration at the bottom sites of S15 The concentrations of dissolved arsenic were fairly uniform dur-
and S16 was above the guideline concentration of 1.3 lg/L applied ing the 2004 study, but exhibited a marginal increase with depth in
to marine waters in Australia (ANZECC/ARMCANZ, 2000). the 2009 study (Supplementary Fig. 1 and Tables 1–3). The average
At the time of sampling mostly fresh ore was being processed concentration for all sites sampled in 2004 was 1.13 ± 0.38 lg/L,
and the current study represents a snap-shot under these condi- while the average concentration of all sites sampled in 2009 was
tions. When the mill is processing stockpiled ore, that may be par- 1.41 ± 0.16 lg/L. There did not appear to be a seawater signature
tially oxidised, dissolved copper concentrations have been from the tailings discharge and the dissolved arsenic concentra-
observed to exceed the guidelines in the bottom Senunu Canyon tions were typical of open ocean waters (Cutter and Cutter, 1995;
waters (Jorina Waworuntu, personal communication). Duan et al., 2010; Ellwood and Maher, 2002). Dissolved arsenic
Dissolved zinc concentrations were in the sub-lg/L range and was also lower than the conservative low reliability guideline con-
fairly uniform at most sites during the 2004 and 2009 surveys centrations of 2.3 and 4.5 lg/L for As (III) and As (V), respectively,
B.M. Angel et al. / Marine Pollution Bulletin 73 (2013) 306–313 311

indicating a low risk of organism toxicity from arsenic exposure The highest concentrations of dissolved manganese measured in
(ANZECC/ARMCANZ, 2000). 2004 were 3 and 6 lg/L at bottom depths of sites S16 and S15,
The concentrations of dissolved cadmium at the Alas Strait, respectively, and during 2009 were 3.6 and 10 lg/L at the bottom
South Coast and Senunu Canyon sites were in the ng/L range and depth at sites S28 and S16, respectively. The sites with the highest
relatively low in both the 2004 and 2009 studies (Supplementary concentrations of dissolved manganese also contained some of the
Fig. 1). A similar trend in the depth profile of concentrations was highest concentrations of dissolved copper and zinc, which is fur-
observed in both studies with dissolved cadmium exhibiting a ther evidence of a localised signature from the tailings in these bot-
clear increase with depth at sites within the Senunu Canyon and tom waters of Senunu Canyon.
at some of the South Coast locations. These depth profiles are con-
sistent with typical nutrient-like depth profile distributions of dis- 3.3. Sediment metal concentrations
solved cadmium in the open ocean, but may also indicate a small
contribution from the tailings plume in the Senunu Canyon. Inputs The concentrations of particulate metals in benthic sediments
of cadmium into nearby seawater are likely to occur because of a determined by aqua-regia digestion are shown in Supplementary
combination of dissolved cadmium in the tailings discharge and Table S3. A similar range of concentrations were measured in the
desorption of cadmium from the tailings sediments as they mix 2004 and 2009 surveys, and all particulate metals except copper
with entrained seawater. Cadmium is likely to be one of the more were less than the sediment quality guideline values (SQG) applied
mobile metals in the tailings plume, as chloride complexation facil- in Australia (ANZECC/ARMCANZ, 2000). Similar concentrations of
itates the partitioning of cadmium into the dissolved phase. The As, Cd, Cr, and Hg were measured at all sediment collection loca-
highest cadmium concentrations were 0.085 lg/L in the bottom tions and in the tailings composite sediments, indicating there
water at site S16 during the 2004 study, and 0.063 lg/L in the bot- was no influence of the tailings discharge on these particulate met-
tom water at site S16 during the 2009 study. The dissolved cad- als. The concentrations of Mn, Pb and Zn at the S01 and S03 sites in
mium concentrations in the tailings liquid ranged from 0.10 to the Senunu Canyon close to the tailings discharge were marginally
0.66 lg/L (Table S2) and given the dilution with seawater, would higher than the other South Coast and Alas Strait sites and similar
indicate that release from the tailings particulates influence the to the tailings composite sediments, indicating the discharge only
dissolved cadmium concentration of sites in close proximity to had a marginal influence on the concentrations of these metals at
the discharge. All dissolved cadmium concentrations were much sites in close proximity to the discharge.
lower than the guideline concentration of 5.5 lg/L applied to mar- Total particulate copper concentrations at sites S01, S03 and
ine waters in Australia (ANZECC/ARMCANZ, 2000). S28 exceeded the SQG high value of 270 mg/kg. The copper con-
The concentrations of dissolved chromium were below the centrations at these sites were similar to those in the composite
detection limit of 1 lg/L at all sites except the S12 and S15 waters tailings sediments (Table S3) and much higher than the other
in the 2004 study, where 2 lg/L was found (Tables 1–3). A lower South Coast and Alas Strait sites indicating sediments in close
detection limit for dissolved chromium was achieved in the 2009 proximity to the discharge may be predominantly sourced from
study, which resulted in concentrations being measured above the tailings discharge causing localised elevation of particulate
the detection limit in all samples. The concentration of dissolved copper. At all other sites the total copper concentrations were be-
chromium was fairly uniform and relatively low at all locations low the lower sediment quality guideline (SQG) value of 65 mg/kg.
and depths and the mean concentration (mean ± SD) for all marine Total metal concentrations provide little indication of the bio-
sites was 0.14 ± 0.06 lg/L. There did not appear to be a seawater availability of metals in sediments (Simpson and Batley, 2007).
signature of dissolved chromium from the tailings discharge. The bioavailability of sediment-bound metals can be measured
The concentrations of dissolved mercury were in the low or through their ability to be assimilated by an organism and may be
sub-ng/L range and uniformly low in waters at all locations and influenced by the solid-phase chemical speciation, i.e. metal binding
depths sampled in the 2004 and 2009 studies (Supplementary with particulate sulfide, organic carbon, and iron and manganese
Fig. 1 and Tables 1–3). The mean concentration (mean ± SD) for (oxy)hydroxide phases. Naturally occurring metals are often present
all marine sites was 0.7 ± 0.4 ng/L, which is typical of open ocean in highly mineralised forms (insoluble in dilute acids such as 1 M
waters (Apte et al., 1998; Gill and Fitzgerald, 1988). The highest HCl) and will be less bioavailable to benthic organisms compared
concentration measured was 1.9 ng/L, at site SC1, which was to anthropogenic metals (Simpson and Spadaro, 2011). For analyses
approximately 500 times below concentrations of Indonesian reg- of eight different tailing materials (unpublished study that included
ulatory concern. The concentration of dissolved mercury in the partially oxidised ore feed materials), the mean (± standard devia-
tailings supernatant ranged from 0.3 to 4.5 ng/L, and there did tion) total copper concentrations were 1250 ± 770 mg/kg, compared
not appear to be a seawater signature of dissolved mercury associ- to 150 ± 120 mg/kg for the concentration extracted in 1 M HCl (10 to
ated with the tailings discharge. 20% of the total). For the sediments at S01, S03 and S28, the 1-M HCl-
The concentrations of dissolved lead were in the sub-lg/L range extractable copper concentrations were below SQG value of 65 mg/
and similarly low at most sample sites in Alas Strait, the South Coast kg and should not cause direct toxicity to benthic organisms.
and Senunu Canyon in 2004 and 2009 (Supplementary Fig. 1 and The behaviour of the organisms is considered a significant factor
Tables 1–3). The mean concentration (mean ± SD) for all marine determining the extent of exposure of an organism and therefore
sites was 0.09 ± 0.16 lg/L, and many sites were below the limit of the magnitude of the hazard and the overall risk the sediment poses
detection (<0.02 lg/L). Dissolved lead was marginally higher at to ecosystem health. Many organisms will avoid sediments with
some sites in close proximity to the tailings plume, but most sites undesirable properties and limit impacts to their populations
had concentrations near or below the detection limit, indicating (Lopes et al., 2004; Simpson et al., 2012). During the operation of
that the tailings plume had a low or negligible seawater signature. the DSTP, the tailings deposition zone within Senunu Canyon is
The concentrations of dissolved manganese were mostly in the likely to remain devoid of most benthic invertebrates due to the
sub-lg/L range and fairly uniform at nearly all sites in the 2009 ongoing deposition of solids. The ability of meiofauna to recolonisa-
survey and were mostly below detection in the 2004 survey (Ta- tion the two mine tailings (400–1000 mg Cu/kg) from Batu Hijau
bles 1–3). The mean concentration (mean ± SD) for all marine sites was investigated by Gwyther et al. (2009) using meso- and micro-
sampled during 2009 was 0.49 ± 0.20 lg/L. Concentrations in the cosms deployed in marine waters at a depth of 15 m. They observed
low lg/L range were measured at two locations in the Senunu Can- that the period of time required for abundances of meiofauna to in-
yon in close proximity to the point of discharge in both surveys. crease from zero to levels statistically indistinguishable from
312 B.M. Angel et al. / Marine Pollution Bulletin 73 (2013) 306–313

natural unaffected controls were twice as long for tailings Appendix A. Supplementary material
(203 days) than for defaunated controls (97 days). Furthermore,
colonisation was well established in tailing from freshly mined Supplementary data associated with this article can be found, in
ore after 40 days, and in tailing from stockpiled, partially oxidised, the online version, at http://dx.doi.org/10.1016/j.marpolbul.2013.
ore after 65 days. That study provided further evidence of the rela- 04.013.
tively low bioavailability of the copper within the tailing materials.
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