SUPPORTING DOCUMENT 14

GIANT MINE
PHYSICAL ENCAPSULATION OF
ARSENIC TRIOXIDE DUST
 SUPPORTING DOCUMENT 14

GIANT MINE
PHYSICAL ENCAPSULATION OF ARSENIC TRIOXIDE DUST

Prepared for:

DEPARTMENT OF INDIAN AFFAIRS AND NORTHERN DEVELOPMENT

PreCambrian Building
Suite 500, 4920 52nd Street
Yellowknife, NT
X1A 3T1

Prepared by:

STEFFEN ROBERTSON AND KIRSTEN (CANADA) INC.

Suite 800, 580 Hornby Street
Vancouver, B.C. V6C 3B6
Tel: (604) 681-4196 • Fax: (604) 687-5532
E-mail: vancouver@srk.com Web site: www.srk.com

DECEMBER 2002
 GIANT MINE
PHYSICAL ENCAPSULATION OF ARSENIC TRIOXIDE DUST

TABLE OF CONTENTS

1. INTRODUCTION .....................................................................................................................1
2. CEMENT ENCAPSULATED SAMPLES................................................................................2
3. BITUMEN ENCAPSULATED SAMPLES ..............................................................................7
4. CONCLUSIONS......................................................................................................................10
5. RECOMMENDATIONS.........................................................................................................11
5. REFERENCES ........................................................................................................................13

LIST OF TABLES

TABLE 1 Unconfined Compressive Strength of Cement Encapsulated Arsenic Trioxide Dust

Samples ..........................................................................................................................2
TABLE 2 Leachate Results from Cement Encapsulated Arsenic Trioxide Dust Samples..............4
TABLE 3 Predicted Arsenic Concentration in Landfill Leachate from Cement Encapsulated
Arsenic Trioxide Dust....................................................................................................6
TABLE 4 Freeze/Thaw Results for Cement Encapsulated Arsenic Trioxide Dust.........................7
TABLE 5 Leachate Results from Bitumen Encapsulated Arsenic Trioxide Dust Samples ............8
TABLE 6 Predicted Arsenic Concentration in Landfill Leachate from Bitumen Encapsulated
Arsenic Trioxide Dust..................................................................................................10

LIST OF FIGURES

Figure 1: Incremental Leaching Rate vs. Time for Cement Encapsulated Dust Samples ...............5
Figure 2: Incremental Leaching Rate vs. Time for Bitumen Encapsulated Dust Samples..............9

LIST OF APPENDICES

APPENDIX A An Investigation into the Cement and Bitumen Stabilization of Giant

Yellowknife Arsenic Trioxide Dust Samples
APPENDIX B An Investigation into the Freezing/Thawing Response of Cement-Stabilized
Arsenic Trioxide Dust Samples

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 GIANT MINE
PHYSICAL ENCAPSULATION OF ARSENIC TRIOXIDE DUST

1. INTRODUCTION

A laboratory program was initiated in March, 2002 to investigate the leaching

behaviour of arsenic from cement and bitumen cylinders. Lakefield Research
conducted the laboratory program. Their report detailing the methodology and
leaching test results is attached in Appendix A.

In summary, nine cylinders each of cement and bitumen were prepared, each
containing a unique amount of arsenic trioxide dust. Dust amounts selected were 0%
(control sample), 10%, 15%, 20%, 25%, 30%, 40%, 50% and 60%. The actual dust
contents were 0%, 11%, 17%, 22%, 28%, 34%, 45%, 57% and 68%, respectively.
Percentages are based on dry weight charge. Cement cylinders were UCS tested at 14
days and 28 days. Cement cylinders containing 0% to 45% had sufficient strength and
were submitted for leaching tests. All nine bitumen cylinders were also submitted for
leaching tests.

A standard tank leaching procedure was employed where each cylinder was
submerged in a tank of de-ionized water. The leachant was removed at set intervals
and analyzed for arsenic. The tank was refilled with fresh de-ionized water at each
interval. Appendix A contains a detailed description of the leaching procedure.

Standard freeze/thaw tests were conducted on three cement cylinders, containing 0%,
17% and 34% arsenic trioxide dust, respectively. The memorandum describing the
test procedure and results is attached in Appendix B.

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2. CEMENT ENCAPSULATED SAMPLES

The 14 and 28 day unconfined compressive strengths of the cylinders are presented in
Table 1. The results show that the cylinders achieved full strength within two weeks
of curing. However, strength decreases as the content of arsenic trioxide dust
increases. This is likely due to the increasing water to cement ratio. Concrete strength
decreases as the water to cement ratio increases (CPCA, 1984). The samples were
prepared such that the cement content remained at 20.5% of the dry weight charge.
However, the nature of the arsenic trioxide dust is such that increasing amounts of
water was required to achieve a workable material. The water to cement ratios for the
cylinders are given in Table 1.

TABLE 1
Unconfined Compressive Strength of Cement Encapsulated
Arsenic Trioxide Dust Samples

% As2O3 Water:Cement 14 Day Strength 28 Day Strength

Dust MPA MPA
0% 0.48 - 28.8
11% 1.1 14.2 11.8
17% 1.25 8.8 9
22% 1.41 4.2 4.8
28% 1.6 2.2 2.3
34% 1.7 1.2 1.3
45% 1.96 0.6 0.6
57% 2.3 0.15 0.16
68% 3.5 too soft for testing 0.07
Prepared by: DDS
Checked by: DBM

Leachate analyses reported by Lakefield Research are presented in Table 2. All

samples produced alkaline leachates; although, the pH decreases with an increasing
amount of arsenic trioxide dust in the cylinder. The pH of leachate from each cylinder
remained relatively constant over time.

As expected, arsenic concentrations in leachate increase as the percentage of dust in

the cylinder increases. Concentration also increased as the amount of time the
leachate contacts the cylinder increased, up to Day 59. Arsenic concentration in the
90 day leachates remained the same or decreased in most samples compared to the 59
day leachates. Concentrations were converted into a daily leaching rate and are
presented in Figure 1. Leaching rate decreased sharply in the first three days, then
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Giant Mine – Physical Encapsulation of Arsenic Trioxide Dust page 3

continued to decrease gradually. The initial high rate is likely associated with a wash-
off effect, where loose surface material and dust directly exposed to the leachant
dissolve relatively quickly. Continued arsenic release from the cylinder is likely the
result of arsenic trioxide dust dissolving into the cylinder pore water and the arsenic
ions diffusing out of the pore water into the leachant surrounding the cylinders. The
decreasing leaching rates observed in the laboratory program suggest that surface area
has not increased, in other words physical breakdown of the cement cylinders was not
excessive.

The diffusion of a constituent from a solid to a liquid can be analyzed in two ways:

1. Fick’s Law. The problem is analyzed using scientific fundamentals and

describing the mechanism using a diffusion coefficient. Fick’s Law is
commonly used when the change in concentration in space and in time is of
interest.
2. Mass transfer coefficient. This gives an approximate engineering description
of the problem. This approach assumes that changes in concentration are
limited to a small volume near the solid/liquid interface and the distance over
which diffusion occurs remains constant.

The information of interest from this study is the mass released from the cylinders and
the relationship between mass released and the leaching condition. The leachate
arsenic concentration change with distance from the cylinder surface is immaterial to
the larger evaluation of remediation alternatives at the Giant Mine site. Observations
by Gjørv (1971) suggest that only a thin surface layer of concrete may become
saturated, even after several decades of continuous submergence. Extrapolating this to
the current testing program, it is expected that the arsenic concentration in the bulk
cement cylinder will remain unchanged. Therefore, a simple calculation using the
initial release rate determined from the experimental data (Figure 1) was used to
predict the arsenic concentration in landfill leachate.

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TABLE 2
Leachate Results from Cement Encapsulated Arsenic Trioxide Dust Samples

Day 1 Day 3 Day 7 Day 14 Day 30 Day 59 Day 90

%
(May 15, 2002) (May 17, 2002) (May 21, 2002) (May 28, 2002) (June 13, 2002) (July 12, 2002) (Aug. 12, 2002)
As2O3
pH Diss. As pH Diss. As pH Diss. As pH Diss. As pH Diss. As pH Diss. As pH Diss. As
Dust
unit mg/L unit mg/L unit mg/L unit mg/L unit mg/L unit mg/L unit mg/L
Control 11.92 <0.05 11.87 <0.05 11.76 <0.05 11.56 <0.05 11.65 0.1 10.14 <0.05 9.86 <0.05
11% 11.38 37 11.35 10.6 11.53 23.7 11.40 19.3 11.75 19.3 11.05 28.8 11.00 25.6
17% 11.24 44.2 11.27 35.2 11.42 41.2 11.29 47.4 10.69 56.4 11.41 43.6 11.41 47.2
22% 10.87 46.3 11.00 57.1 10.81 69.5 11.03 110 10.97 148 11.03 172 10.92 182
28% 10.46 189 10.31 110 10.44 180 10.59 270 10.63 314 10.69 336 10.82 318
34% 10.11 244 10.22 190 10.17 280 10.20 380 10.16 456 10.02 493 10.12 491
45% 9.77 433 9.88 430 9.84 570 9.90 730 9.80 819 9.82 930 9.86 893
Prepared by: DDS
Checked by: DBM

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50.00

45.00
11% Dust
17% Dust
40.00 22% Dust
28% Dust
35.00 34% Dust
Leaching Rate (g As/m2-day)

45% Dust

30.00

25.00

20.00

15.00

10.00

5.00

0.00
0 10 20 30 40 50 60 70 80 90
Time (days)

Figure 1: Incremental Leaching Rate vs. Time for Cement Encapsulated Dust Samples

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The potential impact on arsenic concentration in landfill leachate by the different dust
encapsulation recipes, as represented by the arsenic release rates, was assessed by
calculating landfill leachate concentration as a result of precipitation infiltration
through a degraded cover. A typical performance specification for liner design is a
maximum permeability of 1x10-7 cm/s. When converted to volume this is equal to
0.0864 L/day per square metre of surface area contacted. The arsenic concentration
that will be reached in the leachate can be predicted by:

R SAwaste
As ( g / L) = *
I SAsurface

Where R is the specific arsenic release rate (g m-2day-1)

I is the infiltration rate (0.0864 L m-2 day-1)
and SAwaste/SAsurface is the scaling factor to relate the plan surface
area of the landfill to the reactive surface area of waste.

For the simple calculation presented here, a surface area ratio of 1 was used. This is
the minimum value that would be possible. Table 3 summarizes the resulting arsenic
concentration predictions.

TABLE 3
Predicted Arsenic Concentration in Landfill Leachate from Cement
Encapsulated Arsenic Trioxide Dust

Actual Dust As Release Rate Estimated As As Release Rate Estimated As

Content (1 day leaching) Concentration (90 day leaching) Concentration
% g/m2-day g/L g/m2-day g/L
11 3.7 43 0.083 1.0
17 4.4 51 0.15 1.8
22 4.6 54 0.59 6.8
28 19 219 1.0 12
34 24 282 1.6 18
45 43 501 2.9 33
Prepared by: DDS
Checked by: DBM

The maximum solubility of the arsenic trioxide dust at 10°C is 7.4 g As2O3/L or
5.6 g As/L (see Supporting Document 5). It is clear when comparing that value to the
concentration estimates from Table 3 that landfill leachates will likely be saturated for

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all cement recipes. Even at lower arsenic release rates, saturated leachates can be
expected from most of the cement encapsulated materials.

The freeze/thaw test results are shown in Table 4. The numbers represent the number
of freeze/thaw cycles the sample underwent prior to disintegrating. Twelve cycles are
the maximum number specified by the test procedure. The results clearly indicate that
arsenic trioxide dust content has a negative effect on the durability of cement/dust
mixtures. A contributing factor to the results is likely to be the higher water to cement
ratios in the cylinders containing dust.

TABLE 4
Freeze/Thaw Results for Cement Encapsulated Arsenic Trioxide Dust

Dust Content No. of Cycles

0% >12
17% 2
28% 1
Prepared by: DDS
Checked by: DBM

3. BITUMEN ENCAPSULATED SAMPLES

Bitumen encapsulated arsenic trioxide dust samples were subjected to leaching tests
only. Standard strength tests were not appropriate for the bitumen samples produced
during this study. Freeze/thaw testing was not undertaken due to the inappropriateness
of existing testing protocols. Arsenic concentrations measured in the leach tests are
presented in Table 5 and leaching rates are plotted in Figure 2.

Arsenic leaching rates (Figure 2) show that arsenic release was very low from bitumen
encapsulated arsenic trioxide dust. Arsenic concentrations were relatively constant
with time and dust content (Table 5). Leachate concentrations were assessed using the
same methodology described for the cement encapsulated samples above. The
calculated leachate arsenic concentrations for bitumen samples are presented in
Table 6.

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TABLE 5
Leachate Results from Bitumen Encapsulated Arsenic Trioxide Dust Samples

Day 1 Day 3 Day 7 Day 14 Day 30 Day 59 Day 90

Bitumen (May 15, 2002) (May 17, 2002) (May 21, 2002) (May 28, 2002) (June 13, 2002) (July 12, 2002) (Aug. 12, 2002)
Treatment pH Diss. As pH Diss. As pH Diss. As pH Diss. As pH Diss. As pH Diss. As pH Diss. As
unit mg/L unit mg/L unit mg/L unit mg/L unit mg/L unit mg/L unit mg/L
Control 6.84 <0.05 6.62 <0.05 5.67 <0.05 6.05 <0.05 5.83 <0.05 5.96 <0.05 6.27 <0.05
10% 6.28 0.12 6.05 0.07 5.60 0.11 5.88 0.09 5.63 <0.05 5.94 <0.05 5.96 <0.05
15% 6.29 0.13 6.03 <0.05 5.88 0.08 5.86 0.06 5.58 0.11 5.90 <0.05 5.79 <0.05
20% 6.04 0.08 5.88 <0.05 5.67 0.08 5.85 <0.05 5.56 0.1 5.68 <0.05 5.78 <0.05
25% 6.34 0.14 5.87 0.09 5.66 0.05 5.56 <0.05 5.59 0.06 5.73 <0.05 5.71 0.05
30% 6.16 0.14 5.94 0.14 5.80 0.17 5.46 0.05 5.58 0.1 5.85 0.09 5.73 0.14
40% 6.08 0.29 5.88 0.15 5.79 0.16 5.83 0.06 5.72 0.14 5.86 0.21 5.81 0.35
50% 6.22 0.09 5.97 <0.05 5.73 0.07 5.84 0.07 5.76 0.09 5.86 0.11 5.79 0.13
60% 6.00 0.16 5.97 0.13 5.67 0.12 5.81 0.08 5.81 0.11 5.87 0.15 5.75 0.17
Prepared by: DDS
Checked by: DBM

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0.030

Control
10% Dust
0.025
15% Dust
20% Dust
25% Dust
30% Dust
0.020
Leaching Rate (g/m2-day)

40% Dust
50% Dust
60% Dust

0.015

0.010

0.005

0.000
0 10 20 30 40 50 60 70 80 90
Time (days)

Figure 2: Incremental Leaching Rate vs. Time for Bitumen Encapsulated Dust Samples

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TABLE 6
Predicted Arsenic Concentration in Landfill Leachate from Bitumen
Encapsulated Arsenic Trioxide Dust

Actual Dust As Release Rate Estimated As As Release Rate Estimated As

Content (1 day leaching) Concentration (90 day leaching) Concentration
% g/m2-day g/L g/m2-day g/L
0 0.0050 0.058 0.00016 0.0019
10 0.012 0.14 0.00016 0.0019
15 0.013 0.15 0.00016 0.0019
20 0.0080 0.093 0.00016 0.0019
25 0.014 0.16 0.00016 0.0019
30 0.014 0.16 0.00045 0.0052
40 0.029 0.34 0.0011 0.013
50 0.0090 0.10 0.00042 0.0049
60 0.016 0.19 0.00055 0.0063
Prepared by: DDS
Checked by: DBM

Leachates from the landfilling of bitumen encapsulated arsenic trioxide are unlikely to
be saturated with arsenic; however, arsenic concentrations would certainly be
sufficiently high that treatment of the leachate will be necessary prior to discharge.

4. CONCLUSIONS

Results from the laboratory testing program indicate that cement monoliths containing
up to 34% arsenic trioxide dust will have sufficient strength to remain intact in the
landfill during non-freezing periods. That value could be increased, but would require
additional studies to determine the optimum cement to dust ratio such that the water to
cement ratio in the recipe is reduced to improve the strength characteristics of the
monolith. It is unlikely that arsenic trioxide dust containing cement mixtures
examined in this study would remain intact throughout a winter season. This
behaviour will need to be considered when designing a disposal facility. Leachate
collection and treatment will also be necessary with cement encapsulation. Leachates
from landfills containing cement encapsulated waste are expected to be saturated with
respect to arsenic trioxide dust with a concentration of 5.6 g As/L.

The laboratory program also indicates that bitumen can be an effective encapsulating
agent. However, bitumen containing 50% and 60% arsenic trioxide dust were very
viscous and had to be worked by hand. Therefore, a bitumen mix containing a
maximum of 40% arsenic trioxide dust is recommended if bitumen encapsulation is

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selected for dust disposal. Samples containing up to 60% arsenic trioxide dust
demonstrated good leaching characteristics. Leachates from landfills containing
bitumen stabilized waste are expected to be approximately 350 mg/L.

5. RECOMMENDATIONS

Additional studies will be required if encapsulation of arsenic trioxide dust is selected

as the preferred alternative. For cement encapsulation, the mix recipe would need to
be optimized to achieve acceptable durability during freezing conditions. The
optimization would investigate the proportions of arsenic trioxide dust, cement,
aggregate and water as well as the inclusion of additives. The performance of the new
recipes would be assessed via unconfined compressive strength and freeze/thaw
testing.

Bitumen encapsulation, as envisioned for this project, currently does not have any
precedents. An engineering process would need to be developed and tested to
evaluate the technical feasibility of bitumen encapsulation.

Other types of encapsulating material may be available. For example, a proprietary

technology utilizing a stabilized sulphur-based cement has been tested on dust
containing a relatively low amount of arsenic trioxide. Arsenic concentration in
leachate is reported as approximately 1 mg/L, using the British Columbia Special
Waste Leachate Extraction Procedure. The encapsulating material is also reported to
have undergone 1000 cycles of a freeze/thaw test with minimal degradation. While
these results cannot be directly applied to the conditions at the Giant Mine, the results
are sufficiently promising that this material should be examined further if
encapsulation of the arsenic trioxide dust is selected as a preferred alternative. The
laboratory program would be similar to the one outlined in this report.

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This report, Giant Mine – Physical Encapsulation of Arsenic Trioxide Dust, has
been prepared by:

STEFFEN, ROBERTSON AND KIRSTEN (CANADA) INC.

Diana Sollner P.Eng.

Environmental Engineer

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5. REFERENCES

Canadian Portland Cement Association (CPCA), 1984. Design and Control of

Concrete Mixtures. Engineering Bulletin, Canadian Portland Cement Association,
Ottawa, ON, Canada.

Gjørv, O.E., 1971. “Long-Time Durability of Concrete in Seawater”. ACI Journal,

68-10, pp. 60-67.

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 APPENDIX A

An Investigation into the Cement and Bitumen

Stabilization of Giant Yellowknife Arsenic Trioxide
Dust Samples

(Lakefield Research, 2002)

 APPENDIX B

An Investigation into the Freezing/Thawing Response

of Cement-Stabilized Arsenic Trioxide Dust Samples

(Lakefield Research, 2002)