Marine Pollution Bulletin 56 (2008) 15531569

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Marine Pollution Bulletin

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Heavy metal contamination from gold mining recorded in Porites lobata skeletons, Buyat-Ratototok district, North Sulawesi, Indonesia
Evan N. Edinger a,b,c,*, Karem Azmy c, Wilfredo Diegor c, P. Raja Siregar d
a

Department of Geography, Memorial University, St. Johns, NL, Canada A1B 3X9 Department of Biology, Memorial University, St. Johns, NL, Canada A1B 3X9 c Department of Earth Sciences, Memorial University, St. Johns, NL, Canada A1B 3X9 d Indonesian Forum for the Environment (WALHI), Jl. Tegal Parang Utara No. 14, Jakarta 12790, Indonesia
b

a r t i c l e

i n f o

a b s t r a c t
Shallow marine sediments and fringing coral reefs of the Buyat-Ratototok district of North Sulawesi, Indonesia, are affected by submarine disposal of tailings from industrial gold mining and by small-scale gold mining using mercury amalgamation. Between-site variation in heavy metal concentrations in shallow marine sediments was partially reected by trace element concentrations in reef coral skeletons from adjacent reefs. Corals skeletons recorded silicon, manganese, iron, copper, chromium, cobalt, antimony, thallium, and lead in different concentrations according to proximity to sources, but arsenic concentrations in corals were not signicantly different among sites. Temporal analysis found that peak concentrations of arsenic and chromium generally coincided with peak concentrations of silica and/or copper, suggesting that most trace elements in the coral skeleton were incorporated into detrital siliciclastic sediments, rather than impurities within skeletal aragonite. 2008 Elsevier Ltd. All rights reserved.

Keywords: Submarine mine tailings Arsenic Laser ablation ICP-MS Coral skeleton Porites lobata Indonesia

1. Introduction Retroactive determination of heavy metal concentrations prior to anthropogenic activities is often crucial to understanding the environmental impacts of those activities, particularly in locations where these activities have had a long history. Such retroactive determination is particularly difcult in coastal marine environments, where bioturbation can obscure the temporal record of metals in sediments. Coral skeletons have been used extensively to record the history of metal pollution from dredging, mining, terrestrial runoff, and other sources on coral reefs (Brown and Holley, 1982; Howard and Brown, 1984, 1987; Anderegg et al., 1997; Scott and Davies, 1997; Esslemont, 1999, 2000; Fallon et al., 2002; David, 2003; Runnalls and Coleman, 2003). The ability of corals to record metal pollution varies among metals, due to differences in solubility and differences in the degree to which trace elements can be incorporated into aragonite crystal lattice (Howard and Brown, 1984). Arsenic and mercury, two of the principal contaminants from gold mining, present analytical challenges in this context. The atomic radius of arsenic is incompatible with the dimensions of the aragonite crystal lattice, therefore arsenic incorporated into coral skeletons is thought to be primarily detrital, having entered the coral skeleton as incorporated siliciclastic sediment, rather than
* Corresponding author. Address: Department of Geography, Memorial University, St. Johns, Canada NL A1B 3X9. Tel.: +1 709 737 3233; fax: +1 709 737 3119. E-mail address: eedinger@mun.ca (E.N. Edinger). 0025-326X/$ - see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2008.05.028

as dissolved metal. Mercury presents analytical challenges due to its volatility, which requires distinct analytical techniques for mercury in sediments from techniques used for most other metals. Traditionally, studies of trace elements in coral skeletons have relied upon mechanical sampling followed by chemical analysis using atomic absorbtion spectroscopy (AAS, e.g. Khaled et al., 2003), inductively coupled plasma atomic emission spectroscopy (ICP-AES or ICP-OES, optical emission spectroscopy e.g. Bastidas and Garcia, 1997; David, 2003), or solution inductively-coupled plasma-mass spectrometry (ICP-MS, e.g. Scott and Davies, 1997). Of these methods, ICP-MS is the most sensitive, and has the great advantage of analyzing a wide suite of elements simultaneously (Scott and Davies, 1997). Several recent research efforts relating to coral skeletal records of pollution have used laser ablation mass-spectrometry (LAMICPMS) to reconstruct the history of trace element pollution from coral skeletons (Fallon et al., 2002; Runnalls and Coleman, 2003). Laser ablation has several advantages over traditional analytical methods, including ability to extract precisely located samples from within the coral skeleton, ability to measure concentrations of a wide range of elements simultaneously, and direct introduction of sample to the analytical instrument, thus skipping extensive cleaning, dissolution and possibilities of contamination or operator error associated with wet chemistry (Veinott, 2001). Laser ablation may also introduce some challenges, however. Laser ablation ICP-MS may induce fractionation of some isotopes as the ablation pit becomes deep (Eggins et al., 1998; Gunther

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and Hattendorf, 2001), and laser ablation necessarily mixes latticebound trace elements incorporated from solution with those included within the skeleton as detrital sediment (e.g. Runnalls and Coleman, 2003). Finally, for metals that are heterogeneously distributed within the skeleton, the high spatial precision of off-theshelf laser ablation IPC-MS systems may contribute to high intersample variation that obscures broader patterns. The objectives of this paper are (1) to compare spatial patterns of trace element concentration in marine sediments with those in coral skeletons, and (2) to examine temporal patterns in trace element concentrations in coral skeletons as a historical record of contamination from gold mining activities. We present trace element concentrations and chronologies from Porites lobata corals collected on reefs adjacent to two distinct types of gold mining activities: submarine tailings disposal of industrial gold mine tailings, and small-scale gold mining using mercury amalgamation in coastal watersheds. Our results show that coral skeletons can record trace element contamination from distinct types of gold mining activities, including trace elements that are normally not incorporated into aragonite coral skeletons. In addition, we address two methodological points, (1) comparing whole-sediment and <63 lm sediment trace element concentrations, and (2) assessing the utility of laser-ablation ICP-MS for studying a broad suite of trace element contaminants in coral skeletons. 1.1. Regional geology and mining history North Sulawesi contains signicant gold mineralization in several mining districts. The Buyat-Ratototok mining district (Fig. 1) has experienced mining activity back to the 1920s, with extensive renewed activity beginning in the early to mid-1980s (Turner et al., 1994), and peaking in the late 1980s. Coral reefs fringe much of the coastline, except within protected shallow bays dominated by mangroves, or along sandy beaches.. Geology of the area is reviewed in Turner et al. (1994) and Edinger et al. (2007).

1.1.1. Industrial mine geology and ore processing The Newmont Minahasa Raya (PTNMR) gold mine exploited a refractory sediment hosted deposit with AsSbHgTl anomalies (Turner et al., 1994). Gold within the silicied limestone-hosted deposit is found mostly within ne-grained (<10 lm) arsenian pyrite, typically in the form of pyrite crystals with arsenic-rich rims, co-occurring with antimony suldes and oxides, and mercury sulde. The principal ore body exploited by the industrial mine is >80% refractory gold; gold from this deposit was recovered by roasting and cyanidation (Turner et al., 1994). By contrast, gold in the adjacent Kotabunan and Totok watersheds is present as native gold, and is mined by artisanal miners using mercury amalgamation (Turner et al., 1994; Aspinall, 2001). Whole ore was roasted at 550580 C in the presence of limestone and dolomite from the deposit, with the intent of capturing some arsenic from the host-rock as magnesium arsenate (Weeks et al., 1997). Further milling and processing included cyanidation at pH 99.2, followed by treatment with ferrous sulfate to produce two other arsenic-bearing iron phases, ferric arsenate and arsenical ferrihydrite, and to produce mercuric sulde (Weeks and Wan, 2000). These arsenic and mercury-bearing compounds in the treated tailings were thought to be highly insoluble, but may in fact undergo dissolution at or slightly below the sedimentwater interface (PTNMR, 2002b; Blackwood and Edinger, 2007). Tailings were pumped approximately 5 km from the mine and processing site to Buyat Bay, mixed with seawater, and deposited via pipe 900 m from shore at 82 m depth. While the mill operated, tailings were deposited at approximately 2000 T/day. The mining company commenced a monitoring program upon the opening of the mine in 1996, and modelled the tailings mound as covering an area of approximately 0.32 km2, (PTNMR, 2002a). Mining company monitoring data consistently showed high concentrations of arsenic, antimony, and mercury in mine tailings, but low dissolved concentrations of these metals in seawater above the tailings mound. Tailings disposal was interpreted to pose little environ-

Fig. 1. Location and depth of sample sites. Black line through inset map indicates location of tailings pipe. Artisanal mining occurs in Totok and Kotabunan watersheds. Size of dots indicate depth of sediment samples, coral samples indicated in italics.

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mental danger on the basis of the low dissolved metal concentrations (PTNMR, 2002b), but elevated arsenic and antimony concentrations in shallow marine sediments suggest tailings dispersal at least 1 km northeast, and at least 3 km southeast, of the tailings outfall, in waters as shallow as 20 m (Edinger et al., 2007). Arsenic in tailings includes both geochemically stable and reactive forms, but antimony in tailings is mostly stable (Blackwood and Edinger, 2007). 1.1.2. Small-scale mining Small-scale mining in Indonesia releases large uxes of mercury to air and water, contributing mercury to sh consumed by humans (Kambey et al., 2001; Limbong et al., 2003). In the region of this study, artisanal gold miners operated extensively in the Totok and Kotabunan watersheds (Fig. 1) until approximately 1989, although artisanal gold mining continues to a much lesser extent in both areas. No small-scale mining has occurred in the Buyat River watershed. Concentration of arsenic, cobalt, copper, and other metals in sediments affected by artisanal mining was slightly higher than in regional pre-mining background analyses, possibly due to enhanced erosion associated with mining activities (Edinger et al., 2007). 2. Materials and methods 2.1. Sampling areas Field sampling took place on fringing reefs of Buyat and Totok Bays (Fig. 1). Buyat Bay (approximately 050.40 N/12442.30 E) is a small bay exposed to wave action from the Molucca Sea. The Buyat River debouches at the NW corner of the bay, and a coarse sand tombolo separates Buyat Bay from Totok Bay. The east side of Buyat Bay hosts fringing coral reefs; the reefs closest to the beach are now completely dead, while those monitored by the mining company, in the outer portion of the bay and along the outer margin of the Ratototok Peninsula are in better condition (PTNMR, 2002b). Maximum depth in the bay is approximately 90 m. The shelf remains relatively at until reaching the shelf break at about 120 m depth, roughly 8 km from shore, from which point the bottom descends to bathyal depths (PTNMR, 1994). The shape of the Buyat River mouth, visible plumes of sediment from the Buyat River, and PTNMR current meter data suggest that surface currents generally ow counter-clockwise around the bay. Bottom currents appear to follow a similar pattern (PTNMR, 1994, 2002a, b). Totok Bay (approximately 0520 N/12442.70 E) is a larger bay protected from wave action by the Ratototok Peninsula. Coastlines are mangroves along the protected side of the tombolo separating Totok Bay from Buyat Bay and along the northern margins of the bay, fringing coral reefs along the inner side of the Ratototok Peninsula and the islands in the bay, and cleared mangrove in front of Ratototok village, and adjacent to the mouth of the Totok River. Maximum depth is about 100 m. The shape of sand spits suggests that currents in Totok Bay generally ow in a counter-clockwise direction around the bay. The climate is monsoonal, with a rainy season November to April, and dry season May to October. Sea surface temperatures

range from 27 to 30 C (PTNMR, 1994). Tides in the region are mixed semi-diurnal and microtidal, with a spring tide range of approximately 1.2 m. 2.2. Sediment sample collection and analysis Reef sediments and coral skeletons were collected in June 2002 (17 sediment samples, BY01-18), with further sediment sampling in August 2004 (25 sediment samples, BY21-52). Sediment analysis characterized end-members of sediment in the system, including three primary sources: artisanal gold mining (the Totok River and Kotabunan River) industrial gold mine tailings disposed in Buyat Bay, and the Buyat river, which drains the mine site and has similar bedrock geology to the Totok River watershed (Edinger et al., 2007). Background sediment composition was determined from two sources: the sites furthest to sea in Totok Bay (BY15, BY45 and BY51), and the description of marine sediments collected in 1993 for the industrial gold mines Environmental Impact Assessment (PTNMR, 1994). Sediment samples were collected using a hand-operated PetitPonar grab sampler deployed from a motorized outrigger canoe or shing boat. Position of sampling station positions were recorded using a hand-held GPS. Depth was determined by the length of grab sampler rope; depth measurements associated with grab samples are therefore maximum depth estimates. Visual descriptions of sediment colour, grain size, and bulk composition (carbonate vs. siliciclastic) were recorded in the eld, with subsequent measurement of grain size distribution and carbonate content in the lab. All samples were frozen immediately upon return to shore and kept frozen until analysis. 2.3. Sediment trace element analysis Three gram sediment subsamples were dry-sieved through a 0.063 mm polyurethane mesh to account for grain-size related biases in sediment chemistry. Sediment subsamples were homogenized by stirring, dried, ground to <10 um, and homogenized again for analysis. 2.4. Sediment heavy metal concentrations Concentrations of major and minor elements in the <63 lm fraction of all samples was determined following total dissolution in HFHNO3, measured by inductively-coupled plasma mass spectrometry (ICP-MS). National Research Council of Canada (NRCC) reference materials PACS-1 and MESS-2 were analyzed as unknowns, together with the samples, to monitor data quality (Table 1). Approximately 0.2 g dry subsamples were dissolved in 23 ml of concentrated hydrouoric acid and 8 N nitric acid in 1:1 proportions. Solutions were heated on hot-plates for up to one week, then evaporated to incipient dryness, and diluted to 60 ml with nano-pure distilled water. CaCO3 content of sieved sediments was estimated directly from ICP-MS results, according to the relationship:

%CaCO3 ppmCa 104 1=0:40

Table 1 Sediment solution ICPMS error analysis Measure % Deviation from MESS-2 standard % Deviation from PACS-1 standard Average% deviation among duplicates (n = 4 pairs) %CaCO3 33.6 16.25 5.41 %FeO 2.63 2.90 8.41 Ti 1.34 12.68 3.28 V 12.68 9.28 3.61 Cr 3.23 7.54 8.01 Mn 38.04 33.54 8.89 Co 5.75 6.51 4.35 Ni 43.69 29.66 8.90 Cu 5.82 4.31 3.83 Zn 7.01 0.83 15.84 As 1.61 13.74 2.49 Sb 3.94 8.29 4.12 Pb 2.70 9.01 7.42

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Fig. 2. X-ray negative of coral skeleton BY04L, showing density bands. Approximate track of carbonate sampling and laser ablation analysis indicated by dashed black line. White scale bar 1 cm.

where 0.40 is the weight percent Ca in CaCO3. Although this method could overestimate the carbonate content of sediments by including Ca from volcanic rocks, the weight percent of Ca in calcium carbonate is more than three times that of the weight percent Ca of calcic plagioclase, such that nearly all Ca was probably present as CaCO3. Pre-mining sediment chemistry is reported as the average of 31 marine sediment samples from Buyat Bay and environs, as reported in the mining companys original environmental impact assessment (PTNMR, 1994).

Fig. 3. Scanning electron microprobe images of reef sediments. A. Bioclastic carbonates, tailings-contaminated site BY05. Dark matrix within carbonate clasts is highly similar to tailings-derived sediment observed at tailings outfall and reef BY04. B: Mixed siliciclastics and detrital carbonates, reef near Buyat river mouth, BY07. C. Mixed siliciclastics and detrital carbonates, reef near Totok River mouth, BY14. Bright spots in all images indicate presence of trace elements, esp., arsenic, antimony, barium, copper, chromium, and iron.

Table 2 Sediment (<63 lm fraction) trace element concentrations on reefs sampled Sample characteristics Sample area Buyat Bay affected, protected from wave action Buyat Bay, affected wave exposed reefs Site Reef closest to tailings outfall Tj. Buyat Tj. Sikod (West of bay) Tj. Buyat (East of bay) Bobokan Point Reef near Totok River mouth Reef at Pulau Babi Background sediment Sample # BY04 BY43 BY05 BY08 BY29 BY10 BY07 BY14 BY48 BY15 BY45 Percent %CaCO3 9.78 11.32 18.72 21.39 22.81 25.82 7.52 3.68 4.38 44.48 25.15 %FeO 4.58 4.25 4.15 3.76 3.48 4.26 5.06 5.37 5.74 2.42 4.59 ppm Ti 2744.6 1959.0 2394.1 1770.1 1427.5 1822.3 4093.5 3070.2 3323.4 535.6 2034.4 V 124.5 91.8 108.5 88.1 68.7 85.7 182.4 134.1 143.9 25.8 89.5 Cr 47.0 43.5 41.6 40.7 27.7 26.6 51.9 29.7 34.3 8.3 21.5 Mn 1268.1 1233.6 1081.2 1183.9 866.2 768.6 1330.1 732.9 820.5 205.4 597.7 Co 14.5 9.2 12.0 9.4 6.4 8.9 20.8 14.1 12.7 2.6 9.1 Ni 17.5 14.4 15.2 39.72 8.9 11.4 21.0 16.2 10.9 4.3 9.1 Cu 58.4 37.3 44.2 36.41 18.6 21.7 62.9 44.7 38.0 10.0 26.4 Zn 108.9 80.4 151.3 932.2 86.5 73.3 167.8 112.0 87.8 34.0 59.1 As 253.3 275.4 147.0 194.5 120.6 79.8 61.0 49.3 47.8 5.0 17.8 Sb 164.6 273.5 115.4 164.5 142.0 90.7 18.5 5.7 4.0 1.9 19.2 Pb 12.0 6.7 6.0 8.3 6.3 6.7 5.9 8.9 8.9 2.5 6.7

Buyat Bay, river inuenced Totok Bay, river inuenced Totok Bay reference

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2.5. Coral skeleton sample collection and analysis Domal P. lobata corals were collected whole from approximately 1 m below low tide on seven fringing reefs surrounding Buyat Bay and Totok Bay. Sites BY04, BY05, BY07, BY08, and BY10 were all from fringing reefs surrounding Buyat Bay. Site BY14 is a small fringing reef near the mouth of the Totok River. Site BY15 is a fringing reef on the southwest corner of Pulau Babi, in Totok Bay, approximately 3 km from the Totok River, and serves as a reference site for the Totok River. Coral skeletons were cut in half vertically and air dried in the eld prior to shipment to Canada, where all further analysis took place. Coral skeletons were cut into 810 mm thick slabs parallel to growth lines using a diamond blade rock saw cooled with tap water. Coral skeleton slabs were rinsed with distilled water after cutting, and etched in 0.2 N HNO3 prior to analysis. Each coral skeleton slab was X-rayed to reveal density bands (Fig. 2). For each coral, the slab showing the clearest banding, and for which the cut was most clearly parallel to corallites, was selected for further analysis. Analyses did not follow the axial growth direction of the coral, hence distance between growth bands does not directly reect coral skeletal extension rates (Edinger et al., 2000). 2.6. Coral skeleton stable isotope sampling and analysis To verify that density bands in coral skeletons were annual growth bands, and to assure time control within coral skeletons, d13C and d18O of coral skeleton aragonite were analyzed in coral BY04, and Sr/Ca ratios of coral skeletal aragonite were analyzed in all samples (see below). Small subsamples of skeleton, approximately 320 lg, were drilled from the skeletons along lines perpendicular to growth banding at 2 mm increments. Samples

were reacted in inert atmosphere with ultrapure concentrated orthophosphoric acid at 72 C in a Thermo-Finnigan Gasbench II; the produced CO2 was automatically delivered to a ThermoFinnigan Delta-plus XP isotope ratio mass spectrometer in a stream of helium and measured for isotope ratios. Laboratory standards NBS-18 and NBS-19 were repeatedly measured during each analysis run and yielded a routine precision better than 0.1 per mille. 2.7. Coral skeleton trace element concentrations Coral skeleton trace element concentrations were analyzed using laser ablation-ICPMS. Coral skeleton slabs were cut to 46 23 6 mm (standard thin-section size) blocks for insertion into the laser ablation sample cell. Distance down the coral skeleton was recorded to the nearest 10 lm using the position of the sampling carriage. A NuWave UP 213 nm NdYAG laser system was interfaced to an HP 4500 quadrupole ICPMS with argon as the plasma gas, and helium as the carrier gas. The laser was set to 80 um spot size at 10 Hz, yielding an average beam intensity of 0.5 mJ, equivalent to 11 J/cm2. In all analyses, 44Ca was used as the internal standard. Analyses were conducted on three days: November 14, 2005, November 17, 2005, and August 31, 2006. Each run of 20 analyses included four analyses of NBS 610 glass standard, three analyses of MACS-1 coral aragonite reference material, and at least one duplicate analysis of coral skeleton from the same vertical position within the coral skeleton. In coral BY04, laser ablation spots were matched to the position of the drill holes for carbonate d13C and d18O analyses. Because of the open skeletal nature of P. lobata, analyses did not strictly follow corallite walls. Duplicate analyses were run to check for consistency, and in cases where the initial run displayed signicant yield attenuation.

Fig. 4. Trace element concentrations in sediments (<63 lm fraction).

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Trace element concentrations in coral skeletons were calibrated to the NBS 610 fused glass standard, rather than the MACS-1 carbonate reference material, because there are, as yet, no published certied values for MACS-1. Instead, the MACS standard was used for quality control. The relative standard deviation (RSD) and standard error (sd/n1/2) of each element measured was calculated for the MACS standard, as a measure of the consistency with which the laser-ablated carbonates released each element to the mass spectrometer. The results from the LA-ICPMS analyses of the MACS standard were compared to data obtained by solution ICPMS done in the same lab, using the procedure described for sediment trace element analysis. 2.8. Data analysis Prior to statistical analysis, repeat coral skeleton trace element concentration data were screened to assess variability and to consolidate repeat analyses. Repeat analyses for which the initial ablation signal displayed signicant attenuation were removed. Second, the average of repeat analyses was calculated for pairs that both had consistent yield. Because concentrations of trace elements in coral skeletons appeared non-normal, concentrations were compared among sites using exploratory data analysis (EDA) and the KruskallWallis test. Correlation coefcients among the elements analyzed in all coral skeleton ablations were calcuTable 3 Correlation matrix among elements in sediment Element Ca Ti V Cr Mn Fe Co Ni Cu Zn As Sb Pb Ca 0.67** 0.68** 0.47** 0.37** 0.66** 0.67** 0.47** 0.78** 0.21 0.19 0.47** 0.12 Ti 0.99** 0.49** 0.36* 0.97** 0.98** 0.50** 0.77** 0.43** 0.48** 0.56** 0.26 V Cr Mn Fe

lated using bivariate linear correlation of log-transformed concentrations. Correspondence between metal concentrations in the <63 lm fraction of sediment samples and metal concentrations in coral skeleton bulk analyses was assessed using linear regression between the sediment metal concentrations and the median coral skeleton metal concentrations at each location, as determined from the EDA. Coral Sr/Ca ratios, in mmol/mol were used as a proxy record of sea surface temperature, and to verify the annual nature of skeletal density banding. Because no single isotope of strontium was more or less variable than the others, Sr/Ca ratios were calculated as the average of 84Sr, 86Sr, and 87Sr divided by the average of 42Ca and 43 Ca,

Sr=Ca mmol=mol average84 Sr;86 Sr;87 Sr 1000=average42 Ca and 43 Ca:

3. Results 3.1. Sediment constituent analysis 3.1.1. Sediment carbonate content and mineralogy Carbonate content was approximately 1015% in uvial and river-mouth sandy sediments, 1426% in other marine sediments,

Co

Ni

Cu

Zn

As

Sb

Pb

0.53** 0.38* 0.97* 0.97** 0.53** 0.79** 0.46** 0.48** 0.57** 0.26

0.91** 0.41** 0.47** 0.78** 0.72** 0.40* 0.37* 0.24 0.10

0.21 0.35* 0.74** 0.65** 0.43** 0.54** 0.40* 0.19

0.93** 0.40* 0.68** 0.35* 0.60** 0.66** 0.21

0.55** 0.81** 0.44** 0.50** 0.59** 0.19

0.73** 0.66** 0.21 0.08 0.07

0.51** 0.06 0.27 0.25

0.03 0.03 0.52**

0.93** 0.10

0.11

**

All values ln-transformed prior to calculating correlation coefcients. Arsenic and antimony were highly correlated with each other, and weakly or inversely correlated with most other trace elements. p < 0.01, *p < 0.05. N = 40 in all cases.

Table 4 Comparison between whole sediment trace element concentrations and <63 lm sediment trace element concentrations Element All samples (n = 40) r2
2

Reef-associated samples (n = 14) Coefcient (%) r2 0.87 0.87 0.82 0.83 0.64 0.001 0.76 0.81 0.85 Coefcient (%) 71 106 102 102 106 18 115 112 96

(A) Regression coefcients and r values for comparisons between whole sediment and mud fraction, all samples Ca 0.91 78 Fe 0.88 114 Cr 0.89 96 Co 0.91 104 Cu 0.86 117 Zn 0.14 36 As 0.94 96 Sb 0.94 93 Pb 0.96 113

(B) Factor by which mud fraction sample was elevated above whole sediment sample for reefs from which corals were sampled Bay Site Fe Mn Cr Co Ni Cu Zn Buyat Bay BY04 BY05 BY07 BY08 BY10 BY14 BY15 1.13 1.26 1.07 3.19 1.47 1.04 2.28 1.84 1.76 2.05 5.48 1.52 1.03 1.11 1.32 1.90 1.40 2.81 1.43 0.82 0.8 1.41 1.38 1.36 3.96 1.24 0.87 0.97 1.51 1.61 1.08 9.22 1.01 1.27 0.71 1.99 3.40 2.14 6.69 2.11 0.93 1.30 0.86 2.92 2.10 31.90 1.58 1.22 0.79

As 1.94 2.46 1.98 6.39 1.81 0.75 1.02

Sb 1.01 2.43 1.14 4.0 2.79 1.06 2.04

Pb 1.55 1.17 1.02 2.66 1.66 0.77 1.30

Totok Bay

E.N. Edinger et al. / Marine Pollution Bulletin 56 (2008) 15531569 0.0192 13.67 36.87 52 269.6 37.40 0.467 258.6

1559 Laser d.l.: average detection limit for each element in all laser ablation runs (ppm, except for MgO, Al2O3, SiO2, FeO). Avg, SD, N, RSD, and Sx/Avg refer to laser ablation analyses of MACS-1 pressed coral reference material, referenced to NBS 610 glass standard. All units in ppm unless indicated as percentages. Solution: average results of four solution ICP-MS analyses of MACS-1 reference material. %dev vs. solution: deviation of average MACS ablation result from solution ICP-MS result, expressed as [(avg laser avg solution)/avg solution].

3.2. Sediment trace element concentrations 3.2.1. Sediment sample analytical accuracy and precision Duplicate analyses of identical samples for sediment metal concentrations (n = 4 pairs) yielded results differing by <315% of signal, depending on the element in question, with variation among pairs mostly below 10% (Table 1). Analysis of PACS-1 and MESS-2 standards generally yielded values within 10% of the published valued for one of both standards for all elements except Mn, Zn, and Ag (Table 1). 3.2.2. Spatial patterns in mud fraction sediments Trace element concentrations in the <63 lm fraction of the sediment indicated high concentrations of arsenic and antimony in shallow reef sediments adjacent to the submarine tailings outfall (BY04/BY43, BY05, BY10) and at Tj. Sikod (BY08/BY29), considerably elevated above Totok Bay background concentrations (BY45) or Buyat Bay pre-mining sediment concentrations of those elements (Fig. 4, Table 2). Arsenic and antimony were slightly elevated above background or pre-mining concentrations in uvial and nearshore marine sediments of the Buyat River and river mouth (BY16-BY17, BY09-BY09A) and the Totok River and river mouth (BY18, BY11-14, BY48). Manganese, chromium, and copper concentrations were slightly higher in reef sediments of Buyat Bay than in Totok Bay river-inuenced reef sediments, but iron, nickel, cobalt, zinc, and lead concentrations were approximately equal in the two bays. Titanium and vanadium concentrations were higher in Totok Bay river-inuenced reef sediments and Bobokan reef sediments than in Buyat Bay affected reef sediments (Table 2). Arsenic and antimony were strongly correlated to each other (r = 0.930), and are referred to as tailings metals, while iron, titanium, vanadium, cobalt, and copper were all strongly correlated with one another (r > 0.8), and are referred to as uvial metals. Manganese and chromium were highly correlated with each other, and were weakly correlated with both the tailings metals and the uvial metals (Table 3). 3.2.3. Comparison of whole sediment and mud fraction Trace element concentrations in the mud fraction were strongly correlated with whole sediment concentrations for all elements except Zinc (Table 4A). This pattern held true for all samples analyzed, and for the subset of samples from reef environments, and containing a high biogenic calcium carbonate content. In reef sediments, Ca was 30% lower in the mud fraction than in whole sediments, while all trace elements except Pb were 215% higher in the mud fraction than in whole sediments. At the tailings-inuenced sites dominated by bioclastic reef sediment, particularly BY05, BY07, BY08, and BY10, concentrations of As and Sb in the <63 lm fraction were 1.86.4, and 14, times higher than whole sediment concentrations of these elements, respectively (Table 4B). Concentrations of arsenic were identical in the whole sediment and mud

V Ti %FeO %SiO2 Table 5 Laser ablation ICPMS error analysis %Al2O3 %MgO Measure

Laser d.l. Avg SD N RSD (%) Sx/Avg (%) Solution-ICPMS %dev vs. solution

0.000181 0.00713 0.00701 52 98.33 13.64 0.0000608 50.81

0.000022 0.0923 0.185 52 200.71 27.83 0.00146 76.95

0.0088 0.0856 0.031 51 36.00 5.04 0.000546 241.28

0.00046 0.0256 0.00669 52 26.29 3.63 0.00719 44.4

0.00018 0.00357 0.00753 28 211.2 39.9 0.919 99.6

0.089 0.128 0.170 28 132.99 37.7 1.025 87.5

0.141 128.6 5.95 52 4.63 0.62 100.2 28.26

Cr

0.000011 0.0157 0.00061 52 3.89 0.54 82.95 99.98

Mn

0.068 122.0 4.59 52 3.76 0.64 99.42 22.7

Co

0.458 132.7 11.67 52 8.79 1.66 99.95 32.80

Ni

0.123 119.0 5.09 52 4.27 0.59 94.11 26.41

Cu

0.337 96.6 11.49 52 11.88 1.65 96.50 0.17

Zn

0.348 0.375 0.277 48 73.82 10.66 1.05 64.3

including the tailings, and 1570% in reef sediments (Table 2). Carbonates in reef sediments were easily recognizable as poorlysorted, angular, very coarse-grained bioclasts from corals, calcareous algae and molluscs, while carbonates in uvial and non-reefal sediments were mostly subangular crystalline detrital carbonates (Fig. 3). Most sediment samples were >70% siliciclastic, except BY05, BY07, BY08, BY10, BY15, BY29, and BY51 (Fig. 3; see Appendix 1). Of the siliciclastic samples, most were dominantly siliciclastic mud, except for shallow nearshore samples BY07, BY09, BY11, BY39, BY41, and BY52, collected near the mouths of the Buyat, Totok, and Kotabunan rivers, and samples BY16, 17, and 18, collected in the Buyat and Totok rivers (Table 2, Appendix 1). The samples collected near the end of the tailings pipe were ne silts.

Tl Pb Ba As Sb

0.0431 0.264 0.294 47 111.6 16.28 0.206 27.84

0.113 119.9 7.33 52 6.11 0.85 101.1 18.55

0.0014 112.8 42.83 52 37.98 5.27 98.84 26.33

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fractions of sediments from the two Totok Bay reefs, while antimony concentrations in Totok Bay reef sediments were 12 times elevated in the mud fraction over whole sediment values. 3.3. Coral skeletal metal analyses 3.3.1. Laser ablation and solution ICP-MS analysis of MACS-1 reference material Among the oxides and elements considered here, MgO, Al2O3, Ti, V, As, Sb, and Tl had RSD values greater than 50%, while SiO2, FeO, Cr, Mn, Co, Ni, Cu, Zn, Ba, and Pb had RSD values less than

40% (Table 5). RSD for Sr ranged from 12% to 20%, with the highest value observed in 84Sr, and the lowest in 86Sr. Laser ablation analyses of MACS-1 for SiO2, Ti, V, Mn, As, and Tl differed from solution analyses by 100% or more, while analyses for FeO, Cr, Co, Ni, Cu, Zn, Sb, Ba, and Pb differed from the solution analysis by less than 50%. 3.3.2. Variation in coral skeleton trace element concentrations among reefs Median aluminum oxide concentrations were lowest in corals from exposed, siliciclastic poor sites BY08 and BY10 (Fig. 5A,

0.05
BY14-1

0.50
BY14-1

0.04

0.40
BY07-7 BY14-3

Al2O3 wt %

0.03

SiO2 wt %

0.30
BY04L-4

0.02

BY05-11

0.20

By05-1 BY08-13 BY10-17 BY07-5 BY08-12 BY10-10

0.01
BY05-20 BY04L-31 BY05-19r BY07-16 BY08-40r BY10-17

BY14-5 BY14-21

0.10
BY15-22 BY08-15

0.00 BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15

0.00 BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15

0.35
BY10-01

D
BY10-03

0.12
BY14-1

0.30 0.25

0.10
BY08-8r

0.08

MgO wt %

0.20
BY05-13

FeO wt %

0.06 0.04
By05-1 BY04L-42 BY08-7 BY10-01 BY07-5 BY07-3 BY15-19r

0.15
BY15-13

0.10 0.05 0.00 BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15 0.02 0.00

BY04L-38 BY04L-33

BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15

Fig. 5. Boxplots showing major oxide concentrations in coral skeleton analyses. (A) Aluminum oxide, (B) silica, (C) magnesium oxide and (D) iron oxide concentrations in coral skeletons.

Table 6 KruskallWallis tests comparing trace element concentrations in coral skeletons Element or oxide Al2O3 SiO2 FeO Cr Co Cu Pb As Sb Tl Sediment group Oxides, uvial Oxides, uvial Oxides, Fluvial Fluvial or tailings Fluvial Fluvial Fluvialartisanal Tailings Tailings Tailings Rank order among corals BY05 > BY04 = BY05 = BY14 = BY15 > BY08 > BY10 BY14 > BY05 = BY04 > BY08 = BY10 > BY15 > BY07 BY05 > BY15 > BY08 = BY10 > BY14 > BY04 > BY07 BY04 > BY07 = BY14 > BY05 = BY08 = BY10 > BY15 BY04 = BY08 > BY15 > BY05 > By07 = BY10 > BY14 BY04 > BY15 > BY07 = BY10 > BY05 = BY08 = BY14 BY05 > BY04 = BY08 > BY07 = BY10 > BY14 = BY15 BY04 = BY14 > BY05 = BY07 = BY08 = BY10 = BY15 BY04 > BY14 = BY05 = BY08 > BY07 > BY10 = BY15 BY04 > BY05 > BY08 = BY14 > BY10 = BY15 > BY07 Signicance P < 0.001 P < 0.001 P < 0.001 P < 0.001 P < 0.001 P < 0.001 P < 0.001 P = 0.178 P < 0.001 P < 0.001

Sites: Reef closest to tailings: BY04, Tj. Buyat reef: BY05, Tj. Sikod: BY08, Ratototok Peninsula: BY10, Bobokan Reef (Buyat river mouth): BY07, Totok river mouth: BY14, Reference: BY15. Signicance indicated by KruskallWallis test.

E.N. Edinger et al. / Marine Pollution Bulletin 56 (2008) 15531569

1561

KruskallWallis test, p < 0.001; see Table 6); peak concentrations were highest in coral BY14, near the mouth of the Totok River. Similarly, peak Si02 concentrations were observed in site BY14, followed closely by BY04, closest to the tailings outfall, while median SiO2 concentrations were lowest in corals from exposed sites BY07, BY08, and BY10, and reference site BY15 (Fig. 5B, p < 0.001). Iron oxide concentrations were lowest in corals from reefs BY04 and BY07, highest in coral BY05, and equally abundant in all other corals (Fig. 5C, p < 0.001). Median coral skeleton concentrations of Cr and Cu were highest in coral BY04, closest to the tailings outfall (Fig. 6A, B, p < 0.001), while Zn was highest in corals BY04 and BY14 (Fig. 6C, p < 0.001). Highest peak concentration of Cr was observed in coral BY07, in the plume of the Buyat River, although median concentrations of Cr were higher in coral BY04 than in BY07. Highest Pb concentrations were observed in coral BY05, followed by BY04, BY08, and BY10 (Fig. 6D, p < 0.001). Median arsenic concentrations were statistically indistinguishable in all corals analyzed (Fig. 7A, p > 0.17), but highest peak concentrations were observed in corals BY04 and BY14. Median antimony concentrations were highest in tailings-affected coral BY04, followed by BY05, BY08, and BY14 (Fig. 7B, p < 0.001), and were lowest in uvially-affected coral BY07, exposed site BY10, and reference site BY15. Highest median concentrations of thallium occurred in coral BY04, close to the tailings outfall, followed by exposed tailings-affected sites BY05 and BY08; lowest Tl con-

centrations were observed in uvially-affected corals BY07 and BY14, and in reference coral BY15 (Fig. 7C, p < 0.001). 3.3.3. Trace element correlations in coral skeletons Trace elements in coral skeletons were generally correlated with silica content, with the exceptions of MgO, Cu, Co, and Pb (Table 7). Iron and aluminum were very tightly correlated, consistent with aluminosilicate rocks as a dominant source of iron. Arsenic and antimony, which had extremely high correlations with each other in sediment samples, particularly those affected by industrial mine tailings, were correlated with each other to the same extent as they were each correlated with silica content. Arsenic was signicantly correlated with iron, but antimony was not. 3.3.4. Trace element chronologies in coral skeletons Peak concentrations of arsenic in the Buyat Bay reef coral (BY04) occurred in 1996, the year the mine opened, with secondary peaks in 1997 and 2001 (Fig. 8A). Barium, generally used as an indicator of uvial runoff, showed virtually no temporal variation, and no correlation with As, Sb, Cu, or Cr. Peak concentrations of As and Sb in Tj. Buyat coral BY05 occurred in 1998 and 2000, with a minor peak in 1999 (Fig. 8B). These peaks corresponded with higher concentrations of SiO2 and Cu, but not with Ba, again indicating a correlation with sedimentation, but not necessarily with uvial input. Peak concentrations of Cr in coral BY05 sometimes coincided with SiO2, and sometimes coincided with Ba.

A 10.0
9.0 8.0 7.0

BY07-7

200 180
BY05-6r

160 140

Cu ppm

Cr ppm

6.0 5.0 4.0 3.0 2.0 1.0 0.0

BY04L-26 BY14-3 BY07-14 BY08-33r

BY15-6

120 100 80 60
BY04L-4 BY04L-29

BY05-15

40 20

BY04L-44 BY05-20 BY07-22

BY08-15

BY15-17r

BY08-8r

BY1405

0 BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15 BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15

30
BY04L-4

12.0 10.0

BY05-7

25
BY04L-44

20

8.0
BY04L-29 BY10-17

Zn ppm

Pb ppm

15 10 5 0

6.0
BY04L-30 BY05-6r

By05-1r BY14-1 BY05-17r BY05-7 BY14-13 BY08-17 BY10-14 BY15-16

4.0 2.0 0.0

BY08-35 BY04L-6 BY07-20 BY08-14 BY10-20 BY14-1 BY15-19r

BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15

BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15

Fig. 6. Coral skeleton concentrations of trace elements identied as uvially associated metals in sediment study (Edinger et al., 2007). (A) Cr; (B) Cu; (C) Zn; (D) Pb.

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5.0
BY08-34

4.0
BY04L-47 BY14-21 BY14-1

As ppm

3.0
BY05-8r BY04L-5 BY04L-42 BY05-19r BY08-16 BY08-41 BY10-01

2.0

BY14-22

1.0
BY07-15r

BY15-14

0.0 BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15

1.00 0.90 0.80 0.70

BY04L-4 BY10-07 BY04L-3 BY07-5 BY05-19r BY08-31 BY05-20 BY08-35

Concentrations of As and Sb in Bobokan coral BY07 (near the Buyat river mouth) were generally low, often close to the detection limit for these elements (Fig. 9A). Peak concentrations of Cr in coral BY07 occurred in 1998, 1999, and 2001, and generally coincided with peaks in Ba, SiO2, and Cu. Peak concentrations of As and Sb in coral BY14 (Totok River mouth) occurred in 1998, 1999, and 2001, with additional high concentrations recorded in the two ablations closest to the upper surface of the coral (Fig. 9B). These high concentrations probably resulted from remnant tissue contamination of the material ablated. Peak concentrations of Sb and Cu generally coincided with peak concentrations of SiO2, or to a lesser extent, Cu, but had little apparent relationship with Ba concentrations, except for the elevated As and Sb concentrations in 2001. Concentrations of antimony in reference coral BY15 were generally below detection limits (Fig. 9C). Arsenic concentrations had low peaks in 1998, 2000, and near the top of the coral, but these peaks did not have a clear correspondence with Ba, Cu, or SiO2. Chromium peaks in BY15 were generally associated with minor peaks in silica content. Two major peaks in Cu in 1999 2000 also coincided with increases in silica content. 3.4. Correlations between trace elements in sediments and in coral skeletons Trace element concentrations in sediments (<63 lm fraction) and coral skeletons were generally not signicantly correlated with one another (Table 8). The exceptions to this pattern were antimony, which was weakly positively correlated in sediments and coral skeletons (r = 0.72, p = 0.071), and manganese and cobalt, which were both signicantly inversely correlated in sediments and coral skeletons (Mn: r = 0.84, p = 0.018; Co: r = 0.75, p = 0.05). 4. Discussion

Sb ppm

0.60 0.50 0.40 0.30

BY10-22

0.20
BY07-4 BY15-5

0.10 0.00 BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15

4.1. Nature of trace element incorporation into coral skeleton

0.50
BY04L-14

0.40

Tl ppm

0.30
BY04L-45

0.20
BY04L-13 BY14-1 BY08-33r BY10-05 BY08-36 BY10-21 BY08-21 BY07-20 BY14-11 BY15-2

0.10

BY04L-24 BY05-19r

0.00 BY04 BY 05 BY 07 BY 08 BY 10 BY 14 BY 15
Fig. 7. Coral skeleton concentrations of trace elements identied with industrial mining efuent in sediment study (Edinger et al., 2007). A: As; B: Sb; C: Tl.

Peak concentrations of arsenic and antimony in Tj. Buyat coral BY10 were recorded in 2000, and coincided with a minor peak in Cr, and with mildly elevated concentrations of SiO2, Cu, and Ba (Fig. 8C). Smaller peaks in Sb and Cr co-occurred, and coincided with Cu or SiO2 peaks, but not with peaks in Ba concentration. Peak concentrations of As in Tj. Sikod coral BY08 occurred in 1996, 1997, and 1999, with a minor peak in late 1998 (Fig. 8D). Peak concentrations of As and Cr frequently co-occurred, but peaks in As and Sb did not. Peak concentrations of As generally coincided with peaks in silica content.

Most of the trace elements of greatest concern from gold mining activities in this region are incompatible with the aragonite crystal lattice (Howard and Brown, 1984). Therefore, concentrations of these metals in coral skeletons tend to be lower than metals such as Fe, Cu and Pb, all of which are readily integrated into aragonite skeletons from solution. Concentrations of Cu and Pb in coral BY04 were one to two orders of magnitude higher than concentrations of As and Sb, although in the sediments, As and Sb were an order of magnitude higher than Cu, and two orders of magnitude higher than Pb. Peak concentrations of Fe and Cu frequently coincided in the coral skeleton chronologies. Concentrations of most metals in coral skeleton analyses were correlated with silica, and to a lesser extent, with aluminum oxide, suggesting that most of the trace elements measured were attached to detrital sediment particles incorporated into the coral skeletons, with some component of Cu and Pb from solution. The fact that site BY04 had the highest concentrations of most metals probably results from it having exposure to very ne grained metal-bearing particles, of which most, but not all, were probably derived from the industrial mine tailings. Fine-grained particles are more easily resuspended onto coral reefs, and are more easily trapped within the trabeculae of the coral skeleton (Cortes and Risk, 1985; Budd et al., 1993). The other source of ne-grained particulate related to mining is enhanced erosion and transport of metalliferous rocks associated with mining and road construction (Appleton et al., 2001; Edinger et al., 2007). Surprisingly, peak concentrations of arsenic and antimony generally did not coincide in the coral skeleton chronologies, suggesting that many of the sediment particles incorporated into tailings-affected corals were ne-grained arsenates and antimony oxides, trav-

E.N. Edinger et al. / Marine Pollution Bulletin 56 (2008) 15531569 Table 7 Correlation matrix among elements recorded in coral skeletons, ln-transformed MgO Al2O3 SiO2 CaO_42 CaO_43 FeO Co Cu Zn As Sb Ba Tl Pb 0.060 0.063 0.040 0.016 0.077 0.117 0.068 0.008 0.034 0.016 0.383** 0.32 0.133 Al2O3 0.507** 0.002 0.002 0.646** 0.069 0.005 0.11 0.294** 0.006 0.128 0.155* 0.047 SiO2 CaO42 CaO43 FeO Co Cu Zn As Sb Ba

1563

Tl

0.038 0.165* 0.329** 0.022 0.061 0.258** 0.247** 0.252** 0.141* 0.261** 0.141*

0.534** 0.006 0.002 0.041 0.026 0.143* 0.047 0.144* 0.007 0.022

0.168* 0.037 0.073 0.065 0.151* 0.013 0.087 0.059 0.014

0.09 0.066 0.079 0.215** 0.132 0.308** 0.07 0.171*

0.19** 0.099 0.029 0.027 0.052 0.024 0.034

0.305** 0.000 0.046 0.127 0.109 0.234**

0.142* 0.159* 0.088 0.211** 0.115

0.226** 0.012 0.204** 0.112

0.024 0.280** 0.075

0.052 0.251**

0.067

** p < 0.01, * p < 0.05. N = 207 in all cases.

BY 04 (closest reef to tailings outfall)

2000 2002 2001 1999 1998 1997 1996
SiO /100

2.0 1.6
[As, Sb, Cr]

1.2 0.8 0.4 0.0

Cr

As Sb

Cu
[Ba, Cu], ppm, [Si/100] ppm 20 16 12 8 4 0 -4.5 -5.0 -5.5 -6.0 -6.5 0

Ba
9.5 Sr/Ca mmol/mol 9.0 8.5

8.0 Sr/Ca 7.5 7.0 10 20 30 40 50 60 70 80 90 100

18

vertical distance (mm)

Fig. 8. Coral skeleton trace element chronologies: reef affected by industrial mine tailings. (A) Reef inside Buyat Bay (BY04). (B) Tj. Buyat (BY05). (C) Ratototok Peninsula (BY10); (D) Tj. Sikod (BY08). Annual bands (vertical grey bars) were identied using the skeletal density bands, and veried as annual using Sr/Ca ratios.

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BY 05 (500 m east of tailings outfall)

2002 2001 2000 1999 1998
As SiO /10 Ba 9.5 Cu Sr/Ca mmol/mol 9.0 8.5 8.0 7.5 7.0 5 10 15 20 25 30 35 40 45 50

2.0 1.6 [As, Sb, Cr,] 1.2 0.8 0.4 0.0 [Ba, Cu], ppm, [Si/100] ppm 20 16 12 8 4 0 Sb Cr

vertical distance (mm)

BY 10 (1 km east of tailings outfall)

2002 2001 2000 1999 1998
Si/100 Ba Cu 9.5 9.0 8.5 8.0 7.5 7.0 0 5 10 15 20 25 30 35 40 45

Sb 1.0 0.8 0.6 0.4 0.2 0.0 20 16 12 8 4 0 [As, Sb, Cr,]

Cr As

[Ba, Cu], ppm, [Si/100] ppm

vertical distance (mm)

Fig. 8 (continued)

elling with ne-grained silica from mine tailings, rather than pyrite crystals with arsenic or antimony-rich rims (Blackwood and Edinger,

2007). Amorphous colloidal ironarsenic phases were observed in tailings sediment and in sediments from Buyat Bay reef BY04 and

Sr/Ca mmol/mol

E.N. Edinger et al. / Marine Pollution Bulletin 56 (2008) 15531569

1565

BY 08 (900 m west of tailings outfall)

2002 2001 2000 1999 1998 1997 1996
2.0 1.6 [As, Sb, Cr,] 1.2 0.8 0.4 0.0 [Ba, Cu], ppm, [Si/100] ppm 20 16 12 8 4 0 Cu 9.5 9.0 8.5 8.0 7.5 SiO /100 Ba
4.6 ppm

10

20

30

40

50

60

70

80

90

100

vertical distance (mm)

Fig. 8 (continued)

Tj. Buyat Reef BY05 (Blackwood and Edinger, 2007). However, iron and arsenic peaks did not always coincide in skeletal chronologies, and iron and arsenic were not correlated in coral skeletal analyses from site BY04, suggesting that much of the arsenic in coral skeletons may have been present as Mgarsenate, another tailings processing by-product. Arsenic in Totok Bay reefs was likely present as negrained arsenopyrite (Blackwood and Edinger, 2007); silt-sized grains of arsenopyrite were observed in sediment from both the Totok and Buyat rivers (Blackwood and Edinger, 2007). 4.2. Inuence of grain size on sediment trace element analyses Sediment trace element analysis results for the mud fraction were highly consistent with whole sediment concentrations previously reported for the same sites (Edinger et al., 2007; Table 4). The major differences encountered were at tailings-inuenced sites dominated by bioclastic reef sediment, particularly BY05, BY08, and BY10 (Edinger et al., 2007). The ne fraction sediment data further document dispersal of mine-tailings derived sediment onto reefs 12 km away from the mine tailings outfall (Edinger et al., 2007). The high degree of agreement between whole-sediment and <63 lm fraction analyses reects the immature nature of marine sediments in this region, i.e. derived from recent mechanical erosion and chemical weathering of volcanic rocks. This level of agreement would be unlikely in cases where the dominant sources of metals were dissolved, and metals were adsorbed to mineralogically differentiated clay minerals. Although trace element analysis of the <63 lm fraction of sediments is routine in environmental analyses (e.g. Salomons and Forstner, 1984; and many others), sediment quality guidelines of-

ten apply to whole sediment (e.g. CCME, 2001). Our results emphasize the importance of analyzing the ne fraction of sediments, particularly in mixed carbonate-siliciclastic settings, where coarse biogenic carbonates dilute the trace element signal incorporated into, or adsorbed onto, ne-grained siliciclastic sediments. Revision of sediment quality guidelines to specify analysis of the <63 lm fraction should be considered. 4.3. Evaluation of trace element measurement techniques Coral skeleton analysis with laser-ablation-ICP-MS successfully revealed relative spatial and temporal variation in heavy metal contamination of reefs from industrial gold mine tailings disposal and enhanced erosion associated with artisanal gold mining. Laser ablation ICPMS was effective in quickly and efciently measuring the concentrations of most trace elements in these coral skeletons, and successfully avoided selective dissolution of some siliciclastic phases along with carbonates (cf. Runnalls and Coleman, 2003). Concentrations of most, but not all, trace elements in coral skeletons were well above detection limits for LA-ICP-MS, but might have fallen below detection limits for more traditional approaches like solution AAS or ICP-AES. Nonetheless, comparison of laser ablation analysis of the MACS reference material with solution analyses of MACS suggested that laser ablation gave an incomplete yield for some elements, particularly Ti, V, and As. The high RSD of laser ablation analyses for MgO, Al2O3, Ti, V, As, Sb, and Tl in the MACS reference material suggest an inhomogeneous distribution of these elements within MACS (Table 5). Because MACS is a pressed-powder material composed of aragonite coral skeleton spiked with known quantities of

Sr/Ca mmol/mol

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E.N. Edinger et al. / Marine Pollution Bulletin 56 (2008) 15531569

BY 07 (closest to Buyat river mouth)

2002 2001 2000 1999 1998
2.0 1.6
[As, Sb, Cr,]

1.2 0.8 0.4 0.0

Cr As Sb

[Ba, Cu], ppm, [Si/100] ppm

20 16 12 8 4 0
SiO /100 Ba Cu

9.5 9.0 8.5 8.0 7.5

Sr/Ca mmol/mol

10

15

20 25 30 vertical distance (mm)

35

40

45

BY 14 (closest to Totok river mouth)

2002 2001 2000 1999 1998
10.0 9.5 9.0 8.5 8.0

2.0
[As, Sb, Cr,]

As

1.6 1.2 0.8 0.4 0.0

[Ba, Cu], ppm, [Si/100] ppm
Sb Cr

20 16 12 8 4 0

SiO /100

Cu Ba

10

15

20

25

30

35

40

45

vertical distance (mm)

Fig. 9. Coral skeleton trace element chronologies: reef affected by uvial runoff, artisanal mining, and reference site. (A) Bobokan, near Buyat river mouth (BY07); (B) Totok River mouth (BY14), affected by artisanal mining; (C) Reference site, Pulau Babi, Totok Bay (BY15). Annual bands (vertical grey bars) were identied using the skeletal density bands, and veried as annual using Sr/Ca ratios.

various trace elements rather than a fused homogenized glass, inhomogeneities can be expected, particularly for elements incom-

patible with the aragonite crystal lattice. Similarly, differences in ablation yield between the fused glass standard, the MACS

Sr/Ca mmol/mol

E.N. Edinger et al. / Marine Pollution Bulletin 56 (2008) 15531569

1567

BY 15 (reference)
2002 2001 2000 1999
1.6

[As, Sb, Cr,]

1.2 0.8 0.4 0.0

As Cr Sb

[Ba, Cu], ppm, [Si/100] ppm

20 16 12 8 4 0

Si/100 Ba Cu
9.5

1998
9.0 8.5 8.0 7.5 7.0

2.0

10

15

20

25

30

35

40

45

vertical distance (mm)

Fig. 9 (continued)

Table 8 Relationship between sediment (<63 micron) sediment trace element concentrations and average coral skeleton trace element concentrations Metal Cr Mn Fe Co Cu Zn As Sb Pb Th Linear r2 0.317 0.706 0.167 0.561 0.012 0.030 0.193 0.511 0.008 0.033 Linear p 0.188 0.018 0.363 0.053 0.812 0.710 0.325 0.071 0.846 0.695 Log r2 0.212 0.788 0.148 0.571 0.005 0.000 0.201 0.417 0.030 0.006 Log p 0.298 0.008 0.394 0.043 0.886 0.99 0.313 0.117 0.708 0.578 Sense No trend Neg No trend Neg No trend No trend No trend Pos No trend No trend

N = 7 sites in all cases. Most elements showed no signicant relationship between sediment trace element concentration and mean coral skeleton trace element concentration. The three exceptions to this pattern were Mn, Co, and Sb. Mn and Co both showed signicant negative correlations between sediment trace element concentration and coral skeleton trace element concentrations. Arsenic concentrations in sediment and coral skeleton were positively correlated, but the trend was not signicant.

clair et al., 1998; Fallon et al., 2002, 2003; Sinclair, 2005). Such a modied laser ablation system could probably avoid some of the problems with small-scale spatial heterogeneity observed in this study, as it would average the element concentrations within a wider area. Similarly, drilling out subsamples of coral skeleton for solution analysis (cf. Shen and Boyle, 1989; Bastidas and Garcia, 1997; David, 2003) would likely yield a greater amount of total material, possibly avoiding issues with <100 lm scale variation in detrital sediment incorporation into coral skeletons. A drilled sample approach would also allow partitioning of samples for mercury analysis by cold-vapour AAS (cf. Bastidas and Garcia, 1997). Although the mass spectrometer detected Hg, and gave a yield in counts per second, it was not possible to directly calibrate this yield, because neither the NBS 610 standard nor the MACS reference material have published values for mercury concentration. Acknowledgements We thank the people of Buyat Pantai for hospitality and assistance in the eld, particularly Mansur Lombonaung and family. Bayu Suwarno (Kelola) assisted with 2002 eld work, and Dr. Hanny Tioho (Sam Ratulangi University) assisted with 2004 eld work. Tracey Novak assisted with sediment analysis, Mike Tubrett assisted with LA-ICP-MS analysis, and Pam King and Lakhmali Hewa assisted with solution ICP-MS analysis. Charlie Conway drafted the map. The manuscript beneted from comments by J. Rendell and O. Sherwood. Funded by Memorial University of Newfoundland internal grants and an NSERC Discovery grant to EE. Dedicated to the memory of Father Joseph Stiassny.

pressed-pellet carbonate reference material and the porous aragonitic coral skeletons may also contribute to analytical uncertainty. Lateral variation in detrital material incorporation at a scale of 1001000 lm likely accounted for the high variability in most metal chronologies, and the relatively low repeatability of laser ablation analyses in the coral skeleton samples. Some laser ablation ICP-MS systems have been modied to sample from a larger area (50 500 lm), rather than a discrete circular ablation pit (e.g. Sin-

Sr/Ca mmol/mol

1568

Appendix 1 Sample BY03 BY04 BY05 BY07 BY08 BY09 BY09A BY10 BY11 BY12avg BY13 BY14 BY15 BY16 BY17 BY18 BY21 BY22 BY23 BY24avg BY27 BY28 BY29 BY30 BY33 BY34 BY35 BY36avg BY37 BY38 BY39avg BY40 BY41 BY42 BY43 BY45 BY47 BY48 BY51 BY52 CaCO3% whole 6.45 15.45 46.68 8.04 68.82 8.13 6.04 56.60 6.49 4.53 3.64 5.27 84.02 10.87 8.69 6.40 21.79 26.07 20.14 21.04 18.78 37.91 37.34 20.94 21.19 20.87 23.93 25.56 19.33 13.89 6.94 11.03 5.65 14.72 16.27 40.22 26.04 6.60 30.35 12.08 CaCO3% <63 lm 9.91 14.68 28.08 11.28 32.09 10.85 8.68 38.74 7.45 5.33 5.90 5.52 66.71 9.05 8.53 6.41 20.56 22.55 21.23 20.87 18.05 26.29 34.22 20.39 20.16 20.70 20.17 20.62 22.78 15.53 8.87 13.65 8.35 14.64 16.98 37.73 30.79 6.57 28.44 12.12 FeO% 4.63 4.58 4.15 5.06 3.76 6.04 4.85 4.26 9.54 5.49 5.45 5.37 2.42 6.88 6.41 7.24 2.58 3.96 2.82 2.32 3.36 4.59 3.48 3.43 2.98 4.94 2.83 2.94 3.92 4.44 8.13 5.60 8.09 4.36 4.25 4.59 5.94 5.74 4.48 6.72 Ti 2964.21 2744.58 2394.12 4093.54 1770.07 5107.29 2960.62 1822.26 7185.72 2984.93 2859.79 3070.19 535.60 4854.77 3845.22 4310.52 754.76 1640.44 815.63 538.88 1436.02 2236.25 1427.48 1377.35 1094.99 2600.43 1036.72 1049.41 1706.68 2339.87 6145.51 3468.66 5513.26 2349.57 1958.93 2034.42 2610.38 3323.37 2350.94 5667.31 V 134.40 124.51 108.50 182.40 88.06 239.89 132.41 85.73 364.61 143.65 126.04 134.09 25.79 226.69 157.76 202.15 38.87 74.65 42.87 28.73 71.38 105.91 68.74 70.24 59.78 120.53 54.88 56.44 83.64 106.48 279.14 155.08 254.88 102.71 91.83 89.52 119.62 143.91 105.48 271.16 Cr 52 43.48 47.02 41.55 51.88 40.65 59.88 36.74 26.55 65.14 27.98 26.13 29.68 8.34 52.41 35.07 38.29 32.33 30.84 48.00 35.22 37.91 31.12 27.71 40.52 39.47 38.41 39.18 44.63 50.53 46.12 66.71 52.17 61.82 42.51 43.48 21.47 27.23 34.27 27.25 36.79 Mn 1259.35 1268.12 1081.20 1330.08 1183.90 1707.36 1218.73 768.63 1462.10 712.78 694.26 732.94 205.35 1092.98 812.75 971.48 1115.40 822.56 978.16 1200.07 1040.60 902.23 866.21 1007.02 1014.17 1002.91 1220.96 1228.62 1218.80 1160.22 1221.85 1088.97 1175.85 1092.71 1233.58 597.67 591.85 820.49 662.79 1197.23 Co 16.87 14.50 12.00 20.76 9.35 23.22 17.82 8.88 25.34 15.15 14.67 14.13 2.64 19.45 14.53 16.09 3.93 7.04 3.72 2.84 6.16 9.48 6.44 6.34 5.34 10.15 5.20 4.98 7.67 10.22 21.43 13.70 20.26 10.15 9.16 9.07 13.07 12.72 11.38 19.79 Ni 24.57 17.48 15.18 20.97 39.72 20.02 19.62 11.44 19.60 14.46 13.39 16.18 4.33 18.93 14.24 14.42 11.82 12.16 14.75 9.82 13.07 13.62 8.95 12.87 16.64 14.61 17.35 13.40 15.66 18.56 20.63 15.78 26.86 14.87 14.38 9.05 10.67 10.85 10.55 12.90 Cu 63.53 58.41 44.15 62.88 36.41 67.04 63.41 21.70 56.39 56.14 51.74 44.72 9.97 48.29 40.11 51.43 26.98 24.82 37.97 26.66 29.62 28.24 18.61 27.33 29.20 38.32 27.20 31.63 43.92 41.65 58.32 47.04 54.61 41.21 37.31 26.40 30.40 38.01 32.21 62.36 Zn 95.54 108.88 151.29 167.78 932.20 114.49 97.52 73.31 129.82 99.50 129.16 111.99 34.03 102.85 75.81 89.64 83.23 57.12 94.05 57.34 79.24 127.82 86.48 72.47 76.58 188.22 63.74 71.71 102.61 82.04 136.41 89.80 139.68 77.66 80.41 59.08 64.40 87.79 63.29 398.93 As 132.39 253.29 146.97 61.00 194.41 47.24 46.20 79.77 39.95 34.79 37.80 49.33 4.95 21.11 30.31 44.79 523.73 172.55 548.53 407.07 213.92 89.11 120.57 291.95 353.31 107.55 456.57 579.56 481.96 246.85 23.97 134.50 19.10 203.52 275.40 17.75 14.91 47.76 21.26 48.21 Mo 4.40 4.28 3.71 3.96 3.96 3.54 2.94 1.61 3.77 3.33 3.04 3.96 1.48 1.32 0.87 4.08 2.38 1.86 4.30 2.94 1.86 1.44 1.13 2.20 2.31 1.92 2.12 2.74 2.95 1.89 2.22 2.09 1.27 1.65 1.83 0.79 1.32 2.96 1.40 2.40 Ag 0.854 0.997 0.895 0.691 1.000 0.620 0.530 0.411 0.423 0.369 0.282 0.329 0.058 0.079 0.033 0.433 0.480 0.447 0.179 0.272 0.559 0.340 0.332 0.610 0.654 0.778 0.580 0.448 0.625 0.530 0.131 0.333 0.112 0.604 0.524 0.022 0.013 0.236 0.019 1.670 Cd 4.81 4.33 4.05 4.32 3.76 3.87 3.13 0.90 0.84 0.71 0.39 0.60 0.46 0.09 0.18 0.38 0.54 0.50 0.41 0.34 0.00 0.18 0.04 0.47 0.05 0.82 0.00 0.09 0.87 0.34 0.30 0.49 0.19 0.11 0.04 0.13 0.00 0.06 0.05 1.83 Sn 3.72 3.10 3.12 3.44 2.81 3.19 2.81 0.96 1.56 1.27 0.94 1.13 0.43 0.88 0.71 0.97 0.89 0.59 0.49 0.45 0.01 0.40 0.27 0.67 0.52 0.70 0.17 0.31 0.74 0.56 1.29 0.61 2.22 0.47 0.37 0.79 0.23 0.72 0.60 0.94 Sb 59.96 164.57 115.40 18.52 164.47 12.92 6.79 90.65 5.83 4.49 5.00 5.69 1.90 3.78 7.03 5.90 401.94 240.00 518.34 336.18 331.44 117.00 141.99 324.78 360.77 158.68 363.87 483.85 396.42 234.43 7.64 160.63 6.37 213.69 273.46 19.17 6.04 4.03 7.75 17.92 Pb 6.86 11.98 5.99 5.85 8.25 5.40 5.02 6.71 7.35 9.35 10.77 8.93 2.46 5.10 5.79 9.10 6.96 7.52 8.72 6.15 11.59 24.63 6.26 7.01 7.13 39.63 7.11 8.09 7.13 6.61 5.99 6.81 7.21 6.18 6.70 6.65 7.94 8.94 8.01 112.52 Bi 0.455 0.355 0.352 0.375 0.306 0.285 0.241 0.129 0.229 0.235 0.233 0.172 0.064 0.071 0.081 0.223 0.112 0.104 0.066 0.073 0.075 0.062 0.068 0.089 0.105 0.073 0.058 0.084 0.118 0.084 0.079 0.082 0.049 0.079 0.093 0.071 0.071 0.158 0.075 0.033 Th 1.783 1.306 0.945 1.428 0.655 1.174 1.094 0.599 0.931 1.117 1.287 1.145 0.257 1.180 1.333 1.245 0.318 0.541 0.349 0.228 0.612 0.662 0.436 0.507 0.493 0.765 0.457 0.431 0.759 1.000 1.392 1.063 1.300 0.855 0.874 0.760 0.986 1.206 0.963 0.914

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