Vous êtes sur la page 1sur 10

THIOSALT MANAGEMENT AT NORANDA INC.

, BRUNSWICK MINE,
ONGOING RESEARCH

Bob Butler, Noranda Brunswick Mine


Michael Li, Noranda
Pascale St-Germain, Noranda
Alan Thibodeau, Noranda
Craig Wood, Noranda

ABSTRACT

Brunswick Mine has been involved in a comprehensive research program investigating


site specific aspects of thiosalt management to eliminate its adverse environmental
effects. Minimum annual reagent cost estimates for thiosalt treatment using hydrogen
peroxide and sodium hypochlorite are $400K and $1.5 million respectively. Also,
minimum costs for the use of bicarbonate to buffer the pH depression associated with
thiosalt oxidation in the receiving environment is in the order of $400K annually. A
design of experiment (DOE) research program identified that natural UV radiation,
temperature, DO and water chemistry are key factors influencing the natural oxidation
rate of thiosalts within Brunswick’s water management system. A DOE surface response
model was used to describe the thiosalt oxidation kinetics, which were then used to
develop a predictive oxidation model for thiosalt and pH control of the mill’s reclaim
water system.

RESUME

La mine Brunswick a participé à un vaste projet de recherche sur l'étude des aspects
spécifiques au site pour la gestion des sulfosels dans le but d'en éliminer les effets nocifs
sur l'environnement. Les coûts annuels minimums estimés pour traiter les sulfosels au
moyen du peroxyde d'hydrogène et d'hypochlorite de sodium sont respectivement de 400
k$ et 1,5 M$. De plus, les coûts minimums pour utiliser du bicarbonate pour tamponner
la baisse du pH associée à l'oxydation des sulfosels dans l'environnement récepteur sont
de l'ordre de 400 k$ annuellement. Un programme de recherche basé sur la méthode de
conception de plan d'expériences a identifié que la radiation naturelle UV, la température,
l'oxygène dissous et la chimie de l'eau sont des facteurs clefs qui influencent le taux
naturel d'oxydation des sulfosels à l'intérieur du système de gestion d'eau de Brunswick.
Un modèle de réponse en surface a été utiliséd pour décrire la cinétique de l'oxydation
des sulfosels, ce qui a ensuite servi pour développer un modèle prédictif d’oxydation pour
le contrôle des sulfosels et du pH dans le système de récupération d'eau du moulin.
1.0 INTRODUCTION

Brunswick Mine (Brunswick) is located in northern New Brunswick approximately 32


km southwest of Bathurst.

The sulphide deposit was discovered in 1953, and mining production began in 1964. In
the early 1970’s Brunswick identified that the receiving river into which it discharged
treated effluent experienced periodic pH depression during the spring and fall seasons.
The cause of the pH depression was attributed to the oxidation of the thiosalts contained
in the treated effluent. Effluent treatment at the time consisted of conventional lime
neutralization, which did not have any effect on the thiosalts contained in the discharge.

Thiosalts are sulphur compounds formed during the processing of sulphide rich ores.
They are intermediate products in the conversion of sulphides to sulphates (S2- -> SO42-)
and the quantity generated tends to be a function of the type of sulphide mineral being
processed.

2.0 HISTORIC THIOSALT MANAGEMENT

In the mid 1980’s Brunswick implemented a water management program which utilized
the existing sludge ponds to maximise water retention and promote natural oxidation of
the thiosalts on site prior to lime neutralization and then discharge. Although Brunswick
was able to produce a non-detectable thiosalt level (< 10 mg/l) in its discharge during the
summer months there still were pH effects in the receiving stream during spring and fall.

In the 1970’s and 1980’s the thiosalt levels peaked at 1200 mg/l in the effluent during
winter and would drop to a few hundred mg/l in the summer. Improvements in water
management during the late-1980’s provided increased retention and better thiosalt
oxidation during summer resulting in non-detectable thiosalt concentrations in the site’s
discharge by late spring and summer. Then typically the thiosalt concentrations rose
again in the late fall (see Figure 1).

During the winter there is no detectable thiosalt pH effects in the receiving stream and the
final fate of the thiosalts is dilution in the marine environment. During the winter months
and in the summer (non-detectable thiosalt periods) the downstream pH in the receiving
stream is stable at around 6, with pH depression occurring in spring and again in fall.

Figure 2 shows the pH effects in the receiving stream. The pH effect in August 2001 is
non-thiosalt related.
Thiosalt Concentrations in Effluent
900

800 1995

700 1996

600 1997

1998
500

2001
400

300

200

100

Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Date

Figure 1. Thiosalt Concentration in Effluent

pH at Mouth of Receiving River


7

1995
5
1996

1997
4 1998

2001

3
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Date
Figure 2. pH at Mouth of Receiving Stream
3.0 REGULATORY REQUIREMENTS

In 1998 Brunswick Mine began negotiations with provincial regulatory authorities for the
renewal of its Certificate of Approval to Operate (C of A). A major issue in the
negotiations was the need to manage the seasonal thiosalt pH depression occurring in the
receiving environment. The renewal of the C of A was issued with the stipulation to
address thiosalt effects in the receiving stream. Specifically, Brunswick is required to
implement a water management or treatment process that will have the best potential to
eliminate the thiosalt pH depression in the receiving waters.

Although significant research has been done on thiosalts over the last twenty years there
exists little applicable technology that would address the issue. As such, Brunswick then
developed a four year research program to help understand the thiosalt issues around the
site and identify means to comply with the new C of A condition.

This paper presents an overview of the research Brunswick Mine has initiated in it efforts
to understand the thiosalt issues at the site and to develop a water management program
to address the requirement of no thiosalt pH affect in the receiving water.

4.0 BRUNSWICK’S THIOSALT RESEARCH PROGRAM

Brunswick’s first step in addressing the C of A thiosalt requirement was to review their
existing water management system. Coincidentally, at the same time the mine was also
preparing to implement a new process water reclaim system on the tailings impoundment.
The water management review identified an alternative reclaim option which would use
the mine’s old backfill quarry as a reservoir for the new reclaim water system. The
quarry reclaim option provided an opportunity for the capture and re-circulation of a
significant portion of the thiosalts in the process.

As part of the environmental approval a thiosalt oxidation model was developed, using
field data, to estimate the impact of the new reclaim water system on thiosalt discharge.
The available field data used to develop the model was inconsistent and several years old.
However, the Phase I Thiosalt Model estimated a potential 50 % reduction of thiosalt
discharge from the property.

The projected decrease of thiosalt in the discharge required verification. As well we


wanted to identify other opportunities for further thiosalt reduction.

A research program was designed to provide awareness into the thiosalt issues at
Brunswick. The program provided cost estimates for treatment options, field data to
measure and calibrate future modeling and measure implementation success, and insight
into the phenomenon responsible for thiosalt oxidation within the water system.

At the time Brunswick was contemplating funding research into biological treatment of
thiosalts. However, we wanted to estimate order of magnitude costs for chemical
treatment for comparison prior to funding the biological work. Wasserlauf and Durtrizac
(1982) discussed various thiosalt treatment options, of the processes discussed hydrogen
peroxide and sodium hypochlorite were chosen for testing as they had simplicity of
application.

Also, a multi-tasked research program was implemented to provide insight into thiosalt
oxidation within Brunswick’s water management system. Task I was to complete a
Thiosalt mass balance across the property. This would provide data to validate the Phase
I model prediction and the next version of the thiosalt model, as well as it would provide
us with a base case against which to measure improvements.

Task II was the development of an experimental program designed to identify the key
factors responsible for natural thiosalt oxidation. The Design of Experiment (DOE)
surface response method was used to design experiments that would provide the reaction
kinetics to be used in the development of the Phase II Thiosalt Oxidation.

From this work Brunswick would be able to compare the costs of optimizing the existing
water management system against potential treatment options.

In addition to this originally planned research, in the spring of 2002 Brunswick initiated a
Six Sigma project to optimise thiosalt management.

4.1 Peroxide and Hypochlorite Thiosalt Oxidation Study (Orford, I. 1998)

Chemical treatment tests were performed using external reclaim water containing
approximately 850 mg/l total thiosalts. Two litre samples of water were treated, the
samples were stirred and pH and temperature were measured, and an aliquot was taken
for thiosalt measurement.

For thiosalt destruction, either hydrogen peroxide (34-37% H2O2) or bleach (7-13%
Sodium Hypochlorite) were added to the stirred sample of thiosalt solution and pH was
monitored over 30 minutes. A sample from each of the final solutions was analyzed for
thiosalt and total iron. The Sodium Hypochlorite sample was also analyzed for residual
chloride.

Recognizing that the data is preliminary and for cost comparison discussions only, it
required:
• 0.0028 ml of H2O2 (34-37% soln.) to destroy 1 mg of thiosalt; and
• 0.025 ml of bleach (13% soln.) to destroy 1 mg of thiosalt.
It was noted during the tests that the pH dropped rapidly in the initial 5 minutes
indicating that the majority of the thiosalt destruction occurred within this time frame,
suggesting that very little mixing time is required in a full-scale treatment system.
There was significant residual chloride in the Hypochlorite tests, although there is no
toxicity limit on chloride, the provincial environmental limit on chlorine (Cl2) is 2 µg/l,
which may present a problem.

Based on the reagent consumption from the laboratory study and the annual trends for
thiosalts in the effluent the following cost estimate was developed. A base case of 8
weeks of operation assumes that treatment would be required only during the periods
when receiving stream pH drops below 5 (see Figure 1).

Table 1: Reagent Cost of Thiosalt Destruction

Reagent Costs for Thiosalt Destruction


(To Treat 30,000 lpm for 8 weeks)
Reagent Cost Volume of Reagent Thiosalt Estimated Cost
$/l (ml) per mg mg/l
Thiosalt Destroyed
Hydrogen $0.45 0.002 172 $375,000
Peroxide
Sodium $0.18 0.020 172 $1,500,000
Hypochlorite

In order to ensure that there would be no pH decrease in the receiving stream, up to 12


weeks of treatment may be required. This would result in an increase in the Hydrogen
Peroxide cost by 50% up to $560,000 per year.

Table 2: Reagent Cost Sensitivity

Base Case Case 1 Case 2


172 mg/l Thiosalt 172 mg/l Thiosalt 246 mg/l Thiosalt
30,000 lpm 30,000 lpm 40,000 lpm
8 Wks/Year 12 Wks/Year 12 Wks/Year
Hydrogen Peroxide $375,000 $560,000 $715,000
Sodium $1,500,000 $2,250,000 $4,300,000
Hypochlorite

The Noranda Technology Center (NTC), under a Thiosalt Consortium project, assessed
the feasibility of adding bicarbonate into the receiving stream to buffer the pH drop
associated with thiosalt oxidation (Li., M. and Boucher, J.F., 1999). The addition of
bicarbonate appeared to accelerate bacterial growth in the test solution, which resulted in
a severe depression of dissolved oxygen (DO). Bicarbonate addition was feasible with
preliminary treatment costs ranging between $200,000 and $450,000.
The sensitivity exercise provides some preliminary cost estimates for comparison
purposes. If the remaining research does not identify water management options that will
prevent the pH depression then the treatment options will have to be revisited.

4.2 Task I: Thiosalt Mass Balance Through Property

As part of the quarry reclaim project’s governmental approval, the Phase I mass
balance/thiosalt oxidation computer model was developed to describe the thiosalt
oxidation across the Brunswick property. This model was based on a partial year of
monitoring data collected in 1996. Based on this thiosalt model Brunswick estimated that
the use of the backfill quarry would not only provide improvements in the reclaim water
system, but also provide an opportunity to reduce the site’s thiosalt discharge by about
50%.

However, there was insufficient data to validate the model and the projected
improvements for process changes, at best, would only provide estimates of
improvements. To ensure that future versions of the model could be validated a detailed
thiosalt mass balance monitoring program was initiated on the property in 2000.

In each of the main ponds and diversion channels on the property the following
parameters were measured weekly:
• Flows
• Thiosalts
• Metals
• pH and
• Dissolved Oxygen
• Temperature

4.3 Task II: Experimental Program

The next step was to evaluate the thiosalt oxidation processes across the Brunswick
property. This was accomplished using Design of Experiment (DOE) methodology to
identify the key factors responsible for the natural oxidation occurring on site. Then
using the surface response method (SRM) reaction kinetics for these key factors were
estimated, which were then used in developing and refining the Phase II and eventually
the Phase III thiosalt models.

4.3.1 DOE Test Series I and II - Conclusions

Two series of DOE experiments were conducted to assess the role various natural factors
had in the oxidation of thiosalts. The following parameters were investigated:
temperature, UV light, Fe++ and other metal concentrations (Zn, Cu, Pb), pH and
dissolved oxygen. Of the factors tested UV light, temperature and Fe++ concentration
exhibited the most significant effects in the natural thiosalt oxidation processes. It was
also observed that under low pH conditions, when no iron was present, thiosulphate was
oxidized to sulphate and at high pH the polythionates were converted to thiosulphate.

4.3.2 DOE Test Series III – Conclusions

Based on the results from test series I and II a third DOE experiment was conducted,
which would estimate the kinetic relationships for UV light, temperature and pH. A
kinetic model for thiosalt oxidation was then developed based on the results of the SRM
experiment.

In addition to the kinetic data other observations from the test series III included:
• The rate of thiosalt oxidation increases with higher UV intensity and temperature;
• The rate of oxidation appears minimal between the pH’s of 5 to 7 and is higher at
either a low or high pH;
• Thiosulphate is converted to polythionates at neutral pH; and
• At higher pH the polythionates are converted to thiosulphate.

During test series III a DOE test was conducted outside under normal field conditions and
a laboratory DOE test was run with simulated field conditions. The outside oxidation
rate constants were 37% higher then those of the laboratory DOE, however the thiosalt
oxidation trends were very similar.

4.4 Phase II Thiosalt Oxidation Model

Using the SRM kinetic data a second thiosalt oxidation model was developed by Mike Li
of NTC.

The first test of the Phase II model was to predict the thiosalt oxidation effects in the
reclaim water stored in the backfill quarry. The concentrator requires that the reclaim
water have a minimum pH of 6. To ensure that the 2 million cubic metres of water stored
in the quarry did not drop below pH 6, the model was used to estimate the seasonal
alkalinity requirements to neutralize the effect of the thiosalts. Based on the model’s
alkalinity estimates a soda ash addition system was designed and commissioned.

Calibration of the model was then extended to the Tailings Impoundment and the Bio-
pond. The validation is presented in Figures 3 and 4 for the quarry and the tailings
impoundment. The Phase II Thiosalt Oxidation model was so complex that it required a
dedicated user. With the changing priorities at the mine site the model was temporarily
shelved.
Figure 3. Quarry Model Validation (April/01)

Figure 4. Tailings Model Validation (Jan./01)


5.0 PATH FORWARD

In the spring of 2002 a Six Sigma project was initiated with the goal of reviewing
existing data, finalizing any outstanding research and identifying options for process
changes that will optimize thiosalt management and oxidation. This Six Sigma project is
still underway and the outcome has yet to be summarised.

If it is identified through the Six Sigma project that Brunswick will not be able to prevent
the pH effect in the receiving river then thiosalt research in 2003 will be focused on the
design of a treatment system to chemically oxidize the thiosalts during the critical
periods.

REFERENCES

Li, M. and Boucher. J.F. “Thiosalts Treatment by Bicarbonate Addition, A Laboratory-


Scale Feasibility Study”; Thiosalts Consortium Contract No. 23440-8-1003/001/SQ,
Noranda Technology Centre, March 1999

Orford, I. 1998. Laboratory Report: Destruction of Thiosalts with Hydrogen Peroxide


and Bleach. Internal Noranda Report, August 1998.

Wasserlauf, M. and Durtrizac, J.E. “The Chemistry, Generation and Treatment of


Thiosalts in Milling Effluents – a Non-critical Summary of CANMET Investigations
1976-1982”; CANMET Report M38-13/82-4E, CANMET, Energy Mines and Resources
Canada, 1982