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Emission Estimation
Technique Manual
for

Zinc Concentrating,
Smelting and
Refining

First published in December 1999

 EMISSION ESTIMATION TECHNIQUES
FOR
ZINC CONCENTRATING, SMELTING AND REFINING

TABLE OF CONTENTS

1.0 INTRODUCTION 1
1.1 Context and Use of the Manual 1
1.2 EETs Should be Considered as “Points Of Reference” 2
1.3 Hierarchical Approach Recommended in Applying EETs 3
1.4 NPI Emissions in the Environmental Context 3
1.5 NPI Reporting Requirements 3
2.0 PROCESS DESCRIPTION 5
2.1 General 5
2.2 Concentrating 6
2.2.1 General 6
2.2.2 Grinding 6
2.2.3 Flotation 6
2.2.4 Dewatering 7
2.3 Electrolytic Process 9
2.3.1 General 9
2.3.2 Roasting 9
2.3.3 Leaching 9
2.3.4 Purification 10
2.3.5 Electrolysis 10
2.3.6 Casting 10
2.4 Smelting Process 12
2.4.1 Smelting 12
2.4.2 Refining 12
3.0 ANCILLARY ACTIVITIES AND ASSOCIATED FACILITIES 14
3.1 Ancillary Activities 14
3.1.1 Acid Plant 14
3.1.2 Selenium Removal Process 14
3.1.3 Dross Leaching Plant (Lead and Copper Removal) 15
3.1.4 Cadmium Plant 15
3.2 Associated Facilities 17
3.2.1 Fuel and Organic Liquid Storage 17
3.2.2 Fossil Fuel Electric Power Generation 17
3.2.3 Combustion Engines 17
3.3 Maintenance Activities 17
4.0 LIKELY EMISSIONS 18
4.1 Reporting Thresholds 20
4.2 Reporting Requirements 22

Zinc Concentrating, Smelting and Refining i

 ZINC CONCENTRATING, SMELTING AND REFINING

TABLE OF CONTENTS CONT’

5.0 EMISSION ESTIMATION 23

5.1 Emission Estimation Techniques 23
5.1.1 Engineering Calculations 34
5.1.2 Mass Balance 34
5.1.3 Emission Factors 36
5.2 Acceptable Reliability and Uncertainty 37
5.2.1 Direct Measurement 37
5.2.2 Mass Balance 37
5.2.3 Engineering Calculations 38
5.2.4 Emission Factors 38
5.3 NPI Reporting Steps 39
6.0 EMISSIONS TO AIR 40
6.1 Background 40
6.2 Converter and Smelter Emissions 41
6.2.1 Direct Measurement 41
6.2.2 Mass Balance 41
6.3 Dust and PM10 42
6.3.1 Direct Measurement 42
6.3.2 Emission Factors 43
6.4 Metals in Dust 45
6.4.1 Direct Measurement 45
6.4.2 Emission Factors 45
6.5 Acid Mist 46
6.5.1 Direct Measurement 46
6.5.2 Mass Balance 46
6.5.3 Engineering Calculations 46
6.6 Emissions from Associated Facilities and Ancillary Activities 47
6.6.1 Emission Estimation for Fuel 47
6.6.2 Air Emissions from Fuel and Organic Liquid Storage 48
6.6.3 Air Emissions from Fossil Fuel Electric Power Generation 48
6.6.4 Emissions from Internal Combustion (Stationary) Engines 49
6.6.5 Maintenance Activities - Emission Factors for Solvent Degreasing 49
7.0 EMISSIONS TO WATER 50
7.1 Background 50
7.1.1 Run-off and Erosion 50
7.1.2 Discharge of Treated Process Waters 51
7.1.3 Discharge of Sewage and Domestic Wastewaters 51
7.1.4 Spills to Surface Water 52

Zinc Concentrating, Smelting and Refining ii

 ZINC CONCENTRATING, SMELTING AND REFINING

TABLE OF CONTENTS CONT’

8.0 EMISSIONS TO LAND 53

8.1 Background 53
8.2 Groundwater Modelling - Fates and Trajectories 53
8.3 TSF Seepage 53
8.3.1 Direct Measurement 53
8.3.2 Modelling 55
8.3.3 Mass Balance 55
9.0 EXAMPLES OF APPLICATION OF EETS 59
9.1 Sulfur Dioxide 59
9.1.1 Background 59
9.1.2 Direct Measurement 59
9.1.3 Mass Balance 60
9.1.4 Emission Factors 62
9.2 Cyanide 62
9.2.1 Mass Balance 62
9.2.2 Emission Factors 65
9.3 Carbon Disulfide 67
10.0 BEST PRACTICE 69
10.1 Control Technologies for Air Emissions 69
10.1.1 Concentrating 70
10.1.2 Processing Site 70
10.1.3 Site 71
10.2 Control Technologies for Water Emissions 72
10.3 Control Technologies for Land Emissions 72
11.0 GLOSSARY OF TECHNICAL TERMS AND ABBREVIATIONS 73
11.1 Definitions 73
11.2 Abbreviations 74
12.0 REFERENCES 75
12.1 References Cited 75
12.2 References Not Cited 76
APPENDIX A - SOURCES OF EXISTING DATA 77
A1 Existing Data & Research 77
A2 Process Monitoring 78
A3 Licences & Reporting 78
A4 Approvals Data 79
A5 Regulatory Data 79
A6 Suppliers 79
A7 Inventory 80

Zinc Concentrating, Smelting and Refining iii

 ZINC CONCENTRATING, SMELTING AND REFINING

LIST OF FIGURES, TABLES AND EXAMPLES

Figure 1.1 - Scope of the Zinc Concentrating, Smelting and Refining EET Manual
and its Potential Relationship with Other EET Manuals 2
2.1 - Flotation Circuit 4
2.2 - Electrolytic Process 4
2.3 - Zinc Smelting 4
3.1 - Sulfuric Acid Flowsheet 4
6.1 - Emissions Estimation for Converter and Smelter Operations 41
6.2 - Refined Mass Balance Model 42
8.1 - Bore Hole Arrangement for TSFs 54
8.2 - TSF Water Balance 56
9.1 - Estimating SO2 Emissions 60
9.2 - Mass Balance SO2 Calculations for Example 9.1 61
9.3 - Cyanide Emissions 63
9.4 - Mass Balance Approach to Cyanide Emissions from TSFs 64

Table 4.1 - NPI-Listed Substances Likely to Trigger Reporting, and Proposed

Methods for Determining Threshold Exceedance 18
4.2 - NPI Triggers as Related to Metal Concentration in Ore 21
5.1 - Techniques Available for Estimating Emissions of NPI Substances
from Zinc Concentrating, Smelting and Refining 27
5.2 - Techniques Available for Estimating Emissions of NPI Substances from
Ancillary Activities and Associated Activities 30
6.1 - Particulate Emission Factors for Zinc Smelting 44
6.2 - Uncontrolled Fugitive Particulate Emission Factors for Slab Zinc
Smelting 45
6.3 - Emission Factors for Solvent Emissions 49
7.1 - West Australian Water Corporation Wastewater Treatment Design
Criteria for Total Nitrogen and Phosphorus 52
9.1 - Percentage of Natural Degradation of Cyanide Due to Volatilisation 66

Example 6.1 - Using Fuel Analysis Data 48

9.1 - Mass Balance Technique for Estimating SO2 61
9.2 - Breakdown of Xanthates 68

Zinc Concentrating, Smelting and Refining iv

1.0 Introduction

The purpose of all Emission Estimation Technique (EET) Manuals in this series is to assist
Australian manufacturing, industrial and service facilities to report emissions of listed
substances to the National Pollutant Inventory (NPI). This Manual describes the
procedures and recommended approaches for estimating emissions from facilities
engaged in zinc concentrating, smelting and refining.

The scope of this document is to outline methods that can be used by the zinc
concentrating, smelting and refining industry to:

• Identify which substances they are required to report as part of the NPI; and
• Estimate emissions of NPI substances to air, water and land from their facilities.

This handbook covers the concentrating, smelting and refining of zinc commencing from
the delivery of ore to the processing facilities through to the production of +99% pure zinc,
using either the smelting or the electrolytic process.

It also covers operations that produce zinc concentrate only, and smelting and refining of
zinc from imported concentrate. This manual does not include extraction of ore, which is
covered by the EET Manual for Mining.

Ancillary activities such as an acid plant, cadmium plant, selenium removal, and tailings
storage facility (TSF) are covered in this manual. Associated activities such as power
generation - combustion engines, and fuel and organic storage facilities are covered briefly
in this handbook. These activities are covered comprehensively by separate EET manuals.

The emission of NPI substances from a processing facility’s tailings storage facilities
(TSFs), waste management sites, and sewerage systems are included in the reporting
requirements of the NPI system, and are covered by this manual.

EET MANUAL: Zinc Concentrating, Smelting & Refining

HANDBOOK: Zinc Concentrating, Smelting & Refining

ANZSIC CODE: 2723

The scope of this manual is presented diagrammatically in Figure 1.1.

1.1 Context and Use of the Manual

This manual provides a “how to” guide for the application of various methods to estimate
emissions as required by the NPI. It should be noted that if companies estimate their
emissions using any of the emission estimation techniques within the manual, or
techniques approved by the relevant environment authority, then the data will be
displayed on the NPI data base as being of “acceptable reliability”.

Zinc Concentrating, Smelting and Refining 1

It is recognised that the data generated in this process will have varying degrees of
accuracy with respect to the actual emissions from zinc processing facilities. In some cases
there will necessarily be a large potential error due to inherent assumptions in the various
emission estimation techniques (EETs) and/or a lack of available information of chemical
processes.

This difficulty is well illustrated by the example of emissions of cyanide from tailings
storage facilities. Research in this area undertaken by the WA Chemistry Centre has
shown that, for two TSFs with similar rates of seepage to groundwater, there was no
movement of cyanide into groundwater at one site, while significant contamination of
groundwater was detected for the second site. This dramatic difference was believed to be
a result of a particular site characteristic related to cyanide speciation, mineralogy and pH.

Mining of Ore Zinc Concentrating, Ancillary Activities

• Mining EET Manual Smelting & Refining • Non-Ferrous Metal Ore
Smelting EET Manual
• Explosives Detonation
EET Manual • Chemical Product
Zinc Concentrating, Manufacturing EET
Smelting & Refining Manual
EET Manual

Associated Facilities Transfers

• Fossil Fuel Electric Power TRANSFERS (only emissions from transfers
are reportable to the NPI)
Generation EET Manual
• Fuel & Organic Liquid • Movement of product
Storage EET Manual between facilities
• Combustion Engines EET • Waste disposal to off-
Manual site facilities
• Combustion in Boilers EET • Movement of material
Manual to and from TSFs
• Other

Figure 1.1 - Scope of the Zinc Concentrating, Smelting and Refining EET Manual and its
Potential Relationship with Other EET Manuals

1.2 EETs Should be Considered as “Points Of Reference”

The EETs and generic emission factors presented in this manual should be seen as “points
of reference” for guidance purposes only. Each has associated error bands that are
potentially quite large, eg. based on generic emission factors only uncertainties of 100% are
considered likely. Section 5.0 discusses the general reliability associated with the various
methods. The potential errors associated with the different EET options should be
considered on a case-by-case basis as to their suitability for a particular facility.

Zinc Concentrating, Smelting and Refining 2

1.3 Hierarchical Approach Recommended in Applying EETs

This manual presents a number of different EETs, each of which could be applied to the
estimation of NPI substances. The range of available methods should be viewed as a
hierarchy of available techniques in terms of the error associated with the estimate. Each
substance needs to be considered in terms of the level of error that is acceptable or
appropriate with the use of the various estimation techniques. Also the availability of pre-
existing data and the effort required to decrease the error associated with the estimate will
need to be considered. If emissions of a substance are clearly very small no matter which
EET is applied then no further assessment is required.

The steps in meeting the reporting requirements of the NPI can be summarised as follows:

• For Category 1 and 1a substances identify which reportable NPI substances are used (or
handled by way of their incidental presence in ore or materials, or exceeds the bulk
storage capacity for 1a), and determine whether the amounts used or handled are above
the “threshold” values and therefore trigger reporting requirements;
• For Category 2a and 2b substances determine the amount and rate of fuel (or waste)
burnt each year, the annual power consumption and the maximum potential power
consumption, and assess whether the threshold limits are exceeded;
• For Category 3 substances determine the annual emissions to water and assess whether
the threshold limits are exceeded; and
• For those substances above the threshold values, examine the available range of EETs
and determine emission estimates using the most appropriate EET.

Generally it will be appropriate to consider various EETs as alternative options whose

suitability should be evaluated in terms of:

• The associated reliability or error bands; and

• The cost/benefit of using a more reliable method.

1.4 NPI Emissions in the Environmental Context

It should be noted that the NPI reporting process generates emission estimates only. It
does not attempt to relate emissions to potential environmental impacts, bioavailability of
emissions, natural background levels etc.

1.5 NPI Reporting Requirements

Once this manual has been received it is anticipated that each facility will begin recording
emissions within three months. The substances that require reporting are included in the
NPI Guide, Tables 1 and 2, which have been reproduced (in part) in Table 4.1 of this
manual. Initially facilities need only to report on the substances in Table 1, however it is
anticipated that in the future additional substances in Table 2 will need to be considered.

Zinc Concentrating, Smelting and Refining 3

At the end of each reporting year every zinc concentrating, smelting and refining facility is
required to report these emissions to their state Environment Protection Authority (EPA)
or equivalent body. These reported levels are a summation of individual emissions from
plant sectors, for example only one value for the sulfur dioxide emissions is reported (the
plant total), which represents the summation of all individual emissions across the year
and plant divisions. The EPA will verify that the reported levels are a reasonable estimate
of the actual emissions and will forward the values to Environment Australia where they
will be published on a publicly accessible internet database.

Facilities may undertake “Ancillary Activities” such as the production of sulfuric acid or
precious metal purification, either as a process input or through processing of waste
streams. When estimating emissions, a facility should ensure that emissions are not
“double accounted” (refer to Section 5.0). Process flowsheets should be used to minimise
the potential for this. Similarly a facility needs to account for any emissions from
“Associated Facilities”, which may include organic and fuel storage, and energy
generation equipment.

This manual is structured to allow facilities to work through the manual addressing issues
in a structured and coherent manner.

Likely emissions from facilities are discussed in Section 4.0, while Section 5.0 discusses the
approach to emissions estimation and the methods available.

Sections 6.0, 7.0, and 8.0 address the possible emissions from a facility to air, water and
land, and the EETs likely to be applied by the industry. This approach has been adopted
in order to demonstrate how an EET may be applied to estimate the emissions of a
substance and how this EET can be supported by other EETs. For example, facilities may
choose to use a mass balance approach to their estimation of cyanide emissions. However,
the mass balance EET is likely to be supported by direct monitoring data and emission
factors.

Section 9.0 gives examples of the application of EETs to typical emissions from zinc
concentrating, smelting and refining. Finally Section 10.0 identifies control measures that
can be applied to reduce NPI emissions.

This manual has been prepared by National Environmental Consulting Services (NECS)
for Environment Australia.

The document has been developed for the zinc concentrating, smelting and refining
industry and has been based on the EET Manual for Nickel Concentrating, Smelting and
Refining.

Zinc Concentrating, Smelting and Refining 4

2.0 Process Description
2.1 General

Zinc is found in the earth’s crust primarily as zinc sulfide (ZnS). Uses for zinc include
galvanising of all forms of steel, as a constituent of brass, for electrical conductors,
vulcanisation of rubber and in primers and paints. Most of these applications are highly
dependent on zinc’s resistance to corrosion and its lightweight characteristics.

Australia has more than 20% of the world’s known lead-zinc resources and is the largest
producer and exporter of these metals to the world markets. It also has some of the largest
mines for these metals in the world, with major deposits located at McArthur River in the
Northern Territory, Century in Queensland, and the Cannington deposit also in
Queensland. Smaller deposits of lead and zinc are located in the Lachlan Fold Belt in
South-eastern NSW/Northwest Victoria, the Cobar district in NSW, Rosebery in
Tasmania, and at the Woodcutters mine south of Darwin in the Northern Territory.
Refined zinc is exported to a broad range of Asia-Pacific countries and most concentrates
go to Japan and Korea.

At the mine sites the ore minerals are liberated and concentrates are produced. The
concentrates undergo further processing in order to produce zinc as a pure metal. The
two main processes are electrolytic and smelting. Both of these methods begin with the
conversion of sphalerite (zinc sulfide) to zinc oxide via an oxidising roast.

Primary refined zinc is produced at three plants: Risdon (Tasmania), Cockle Creek (NSW)
and Port Pirie (South Australia). The Risdon and Port Pirie refineries use the electrolytic
process, while Cockle Creek, near Newcastle in NSW, uses smelting. At Cockle Creek zinc
is produced from the ISF furnace. The ISF furnace vaporises the zinc, which flows out of
the furnace with the hot gases into a condenser. Within the condenser, the vapour is
contacted with molten lead, which absorbs the zinc. This lead/zinc solution is passed
through a series of cooling channels. As the temperature decreases the zinc floats on the
molten lead and can be collected. The purity of the zinc is refined by distillation in
columns, to produce zinc with a purity of up to 99.95%.

The first step in the electrolytic refining process is the removal of sulfur. The Risdon
refinery roasts the concentrate to form zinc oxide and the Port Pirie refinery oxidises the
slag (containing zinc) from the lead blast furnace. The zinc oxide (and some ferrites) are
leached under acidic conditions to create a zinc sulfate solution. After purification of this
solution, to remove dissolved metals, the solution undergoes electrolysis where zinc is
deposited on aluminium cathodes. Production of secondary refined zinc occurs at Port
Kembla (NSW). Zinc oxide and zinc dust is produced from scrap zinc at West Footscray
in Melbourne (Victoria) and a smaller amount in Brisbane (Queensland).

Distinct processes are applied to the concentrating, smelting and refining of zinc.
Representative processes are discussed below and example process flowsheets are
presented as a source of reference. Facilities are advised to use their own process
flowsheets to assist in structuring and addressing NPI reporting requirements.

Zinc Concentrating, Smelting and Refining 5

Some lead mines produce concentrate only, for smelting elsewhere, or may be fully
integrated, producing final lead product from ore on-site. Thus, not all sections of this
manual will be relevant to each facility. Facilities as not expected to report on substances
they do not emit or produce, nor on processes that they do not undertake.

2.2 Concentrating

2.2.1 General

At the mine site the ore is drilled and blasted in large volumes, often transferred to
underground rock crushers by large loaders before being hoisted to the surface in skips or
driven via trucks. At the surface the ore is subjected to additional crushing and fine
grinding. The first stage of separation sees the separation of zinc and other valuable
sulfide minerals from the waste rock particles to form a concentrate. The zinc sulfide
concentrating process is presented in Error! Not a valid bookmark self-reference..
Concentrating is often carried out in a flotation cell of which there are a number of types.

2.2.2 Grinding

Crushed ore is ground in autogenous and ball mills to further reduce the particle size and
aid in the separation of gangue. The ore is directed to a flotation circuit where lead ore is
first separated while the zinc ore is suppressed. The zinc ore is then returned and floated.

2.2.3 Flotation

Ground zinc ore and water are combined in a series of flotation cells where chemical
reagents (an activator, a collector, a pH modifier and a depressant) are added and mixed,
and air is then injected into the cells. The activator promotes flotation of the slower
floating ferrites while the collector changes the surface of different minerals allowing the
pyrite and zinc-rich particles to attach to the air bubbles and float to the surface of the
liquid forming a froth. The pH modifier helps produce a higher grade of concentrate by
discriminating between which particles attach themselves to the air bubbles and the
depressant suppresses the attachment of certain minerals to the air bubbles so that only
selected compounds will float. The froth, which floats to the surface, contains the majority
of the zinc and iron sulfides. The tailings, which contain the waste minerals, are
transferred to a scavenger cell, which separates any residual zinc composite from the
tailings and recycles them to the flotation cell.

The gangue minerals are unaffected and pass through the flotation cells and are disposed
of as residue, usually in a purpose-built facility, or they may be returned to the mine as
backfilling for mined-out areas.

Although there are common reagents used in flotation cells, it is recommended that each
processing facility refer to their own process flowsheets to identify which reagents are
used and any possible compounds that may form.

Zinc Concentrating, Smelting and Refining 6

2.2.4 Dewatering

Dewatering is conducted in two stages, thickening and filtration. The froth is skimmed off
the top of the cell and the resulting zinc sulfide rich solution is thickened. The thickened
flotation concentrates are then filtered using larox filters. This process increases the grade
of the ore, which may contain only 6% zinc, to a concentrate assaying at more than 50%
zinc. Up to 90% of the zinc in the ore can be recovered using this method.

The moisture content of zinc concentrate is typically 7.2%, and the concentrate is often
sprayed with a dust suppressant as it leaves the mine site.

Zinc Concentrating, Smelting and Refining 7

Figure 2.1 - Flotation Circuit

CONCENTRATING ZINC ORE

INPUTS PROCESS POTENTIAL EMISSIONS
Crushed Ore PM10
Grinding
Metals
1. Activator (Copper Sulfate)
2. Collector (Cyanamids 7016 or
Flotation Activator Products
dithiophosphate,
xanthates) Cells Carbon Disulfide
Flotation Reagents
3. Modifier lime
4. Iron depressant (Polyacrylamide,
sodium cyanide)

Nitric acid PM10

Thickeners Scavengers Cyanide
Hydrogen peroxide Metals

Filtration

Tailings and Sand for backfill Cyanide complexes

Coherex binding agent Zinc Sulfide Slimes to or tailings dam
concentrate (>50%) tailings dam

Zinc Concentrating, Smelting and Refining 8

2.3 Electrolytic Process

2.3.1 General

Electrolytic processing consists of 5 basic steps, roasting, leaching, purification, electrolysis

and casting (refer Error! Not a valid bookmark self-reference.).

2.3.2 Roasting

Roasting is a pyrometallurgical process that converts zinc sulfide concentrate to an impure

zinc oxide (a calcine). The following reaction occurs during roasting:

2ZnS + 3O2 Í 2ZnO + 2SO2

Iron in the concentrate also oxidises and reacts with a portion of the zinc to form zinc
ferrite:

2FeS + ZnS + 5O2 Í ZnO.Fe2O3 + 3SO2

The sulfur is liberated as sulfur dioxide (and a small proportion of sulfur trioxide). The
gas is typically passed through a waste heat boiler followed by a wet scrubber where most
of the remaining calcine dust is removed in the wash water. The gas stream then passes
through electrostatic mist precipitators where the final traces of calcine dust are removed
and delivered to the calcine collecting system. Finally, gas from the precipitators is
delivered to the gas flues leading to a Sulfuric Acid Plant (discussed further in Section 3.1).
The sequence and type of unit operations used in sulfuric acid plants varies between
facilities, for example Pasminco Hobart utilised cyclones to remove the dust. It is
imperative that facilities use the included flowsheets only as guides, and make final NPI
reports in relation to their own facility-specific flowsheets.

2.3.3 Leaching

Zinc in the calcine is present mainly as zinc oxide and zinc ferrite, with small quantities of
zinc sulfate and sulfide. Zinc oxide dissolves readily in relatively weak acid, whereas
significantly more reactive conditions are necessary to dissolve zinc ferrite.

Leaching of the calcine uses spent electrolyte (sulfuric acid) from the electrowinning cells.
After passing through a series of leaching tanks an impure zinc sulfate solution is
produced, which then enters the purification stage. The zinc oxide reacts with the sulfuric
acid according to the following formula:

ZnO + H2SO4 Í ZnSO4 + H2O

ZnO + 2(H3O+) Í Zn2+ + 3H2O

Zinc Concentrating, Smelting and Refining 9

The undissolved zinc ferrite is then reacted with hot concentrated sulfuric acid to form a
zinc and iron sulfate solution.

A number of products and residues may be recovered in the leaching stage. A lead/silver
rich slurry is removed for processing in zinc smelters. The dissolving of zinc ferrite means
that iron, the major impurity in the calcine, is also in solution. This is removed by adding
neutralizing and adding calcine so that the iron is precipitated as paragoethite, which can
be treated off-site. Gypsum is produced from the basics and clean gypsum plants.

Other minor impurities such as copper, cadmium, cobalt, nickel, arsenic and antimony
also enter the solution. All must be removed before the solution goes to the electrolytic
cells. Arsenic, antimony and a number of other trace elements are co-precipitated with
iron, whilst the remaining metals require further purification stages.

2.3.4 Purification

Purification of the zinc sulfate solution is achieved by removing the additional metallic
ions. This is achieved by displacing the metal ions through the addition of zinc dust.
Copper is recovered as a copper sulfate by-product and cadmium as metal is also
recovered for sale. Filter cake, which contains cobalt, nickel, lead and zinc, is sold for
further processing.

2.3.5 Electrolysis

The zinc liquor is piped to electrolytic cells, where the zinc is electrochemically plated on
to aluminium cathodes (electrodes). Approximately two thirds of the zinc in the liquor is
deposited, with the remainder being recycled to the leaching stage in the spent electrolyte.
During electrolysis, when the rich liquor is depleted of a portion of zinc, sulfuric acid is
regenerated within the cell. Manganese mud (electrode slime metal complex) is produced
at the anode and accumulates in the cell requiring periodic removal.

2.3.6 Casting

The zinc is removed from the cathodes, washed, dried, melted in a furnace, and cast into
ingots. A portion of the molten zinc is air atomised with subsequent collection of the dust
by air cyclone and baghouse. Zinc dust is subsequently used in the purification stage.

Zinc Concentrating, Smelting and Refining 10

Figure 2.2 - Electrolytic Process
ZINC ELECTROLYTIC PROCESS
INPUTS PROCESS POTENTIAL EMISSIONS
PM10
Zn Concentrate Roast Gas
Roasting Acid Plant SO2
Natural Gas
Calcine
Sulfuric Acid
H2SO4 Leaching Lead residue
Limestone Gypsum Metals
ZnO dust
Spent Electrolyte

Purification Purification Copper sulfate

Zinc dust
t (cementation) Cadmium

Rich liquor

Acid mist
Electricity Electrolysis Electrode slime
(metal complexes)

Electricity or Natural gas Metallic fume

Casting
Flux (ammonium chloride) PM10

Zinc and Alloys

Zinc Concentrating, Smelting and Refining 11

2.4 Smelting Process

2.4.1 Smelting

The Imperial Smelting Furnace (ISF) process is used to produce zinc and lead metal
simultaneously in a blast furnace. Error! Not a valid bookmark self-reference. displays
this smelting process. Zinc and lead concentrates, from various mines, are blended and
sintered (heating in an oxygen rich environment) to combine the fine particles into lumps
and remove the sulfur as sulfur dioxide, thus oxidising the lead and zinc.

The sintered product is mixed with hot coke and smelted in a blast furnace to produce zinc
vapour (gas), molten lead, and slag. The zinc vapour passes out of the blast furnace with
the furnace gasses into a condenser where the stream is cooled with a spray of cool molten
lead. The lead absorbs the zinc vapour, after cooling the lead and zinc layers separate
giving impure molten zinc metal (98.3% Zn).

2.4.2 Refining

The zinc metal produced by the smelter is not pure and contains small quantities of other
high boiling point metals such as lead, iron, copper and tin. Most of these metals are
removed in the refining process. Zinc may be refined using a distillation process. This
process involves reboiling and recondensing the metal, so as to systematically remove the
impurities. The slag from the furnace will also contain zinc, which may be oxidised and
refined by distillation. After the impurities have been removed the molten zinc can be cast
into ingots or bars.

Zinc Concentrating, Smelting and Refining 12

Figure 2.3 - Zinc Smelting

SMELTING

INPUTS PROCESS POTENTIAL EMISSIONS

Concentrate Metal vapours

Sinter gases PM10
Fuel Sinter Plant Acid Plant
Secondary materials sulfuric acid
SO2
(dusts, residues)
Slurry recycles
Sulfuric Acid

Zn vapour
Condenser
Preheated coke
Briguettes (Sodium silicate binder) Carbon monoxide
Metallic recycles ISF Blast Metal vapours
Fuel Furnace Molten lead PM10

Zinc 98.5%
pure

Slag Lead Bullion

Zinc Concentrating, Smelting and Refining 13

3.0 Ancillary Activities and Associated Facilities

A number of by-products from zinc refining can be converted into saleable products
through ancillary activities. The sulfur dioxide gas released during the sintering process
can be used to produce sulfuric acid, while lead bullion and copper sulfate are recovered
from the smelting process. Finally, cadmium, as well as zinc, is recovered in the refinery.
When the zinc is refined using the roast/leach/electrowin process the anode slimes, which
are deposited in the electrolytic cell, can be purified to recover precious metals such as
gold and silver.

A zinc smelter and refinery may have a number of associated facilities. These facilities can
also produce NPI reportable emissions. Such facilities may include fuel and organic liquid
storage and power generation.

3.1 Ancillary Activities

3.1.1 Acid Plant

A significant environmental problem faced when smelting and refining zinc from sulfide
ore is the formation of sulfur dioxide gas. There are two methods of removing the gas,
either through direct venting or the formation of sulfuric acid. Under current guidelines
the formation of sulfuric acid is encouraged, owing to the adverse environmental effects of
sulfur dioxide gas. The hot gases emitted during sintering, will contain dust. To remove
this dust the gas is typically initially cleaned, which can be conducted using hot gas
precipitators followed by a sequence of wet scrubbers. Final cleaning may be conducted
using wet electrostatic precipitators.

After cleaning the gas is passed dried to remove water then passed to the converter
(or series of converters with intermediate heat recovery) where the sulfur dioxide is
catalytically converted to sulfur trioxide. The sulfur trioxide is dissolved in an absorber to
form sulfuric acid (refer to Error! Not a valid bookmark self-reference.). This sulfuric
acid can be used within the plant or may be sold. It is acknowledged that the described
process may not be the process in place at some facilities. As the flowsheets incorporated
into this manual are generic it is important for facilities to refer to their own process
flowsheets.

The sulfuric acid process comprising the drying towers, converters, heat exchangers and
absorption towers is often referred to as the contact acid process, and the resultant acid
(approximately 98% sulfuric acid) is often referred to as contact acid.

3.1.2 Selenium Removal Process

Several of the zinc concentrates refined in Australia contain selenium, which accumulates
in the electrostatic mist precipitator dust. Selenium is removed as dust and fume from the
hot gas precipitators. The dust is heated with a strong sulfuric acid and the selenium is

Zinc Concentrating, Smelting and Refining 14

extracted as selenium dioxide fume. This fume is then scrubbed with water to produce
selenious acid and crude selenium is recovered by precipitation.

3.1.3 Dross Leaching Plant (Lead and Copper Removal)

When zinc is smelted lead and slag flow from the lower portion of the furnace to dross
kettles. The slag overflows and is granulated with water sprays. The lead, which also
contains copper, silver and gold, is transferred to kettles where it is cooled. This allows
separation and removal of a copper–lead dross, which is screened with the fine fraction
transferred to a leaching plant for recovery of copper as copper sulfate. The lead bullion is
cast into ingots.

3.1.4 Cadmium Plant

Cadmium is a minor constituent in most sinter feed materials. If the sinter gas is
processed through an acid plant some of the cadmium is volatilised and can be collected
from the hot gas precipitators, wash towers and electrostatic mist precipitators. The fume
is leached, washed and passed through ion exchange columns for cadmium removal and
trommelled to recover cadmium. The crude cadmium from this operation is melted,
partially refined, cast and then remelted with cadmium/zinc alloy in the refinery and
distilled in a small refluxing column.

Zinc Concentrating, Smelting and Refining 15

Figure 3.1 - Sulfuric Acid Flowsheet
SULFURIC ACID PLANT
INPUTS PROCESS POTENTIAL EMISSIONS

Dust containing selenium

Hot gas from sinter machine and cadmium
Gas Cleaning
Fume - metal compounds

Mercury precipitation
Hg product
Reagent Mercury Removal
Mercury compounds

Waste water to
Drying Towers settling pond

SO2 to stack
Dilute Converter
sulfuric acid Catalyst residue

Absorption SO2 to stack

Acid Cooler
and Storage

Zinc Concentrating, Smelting and Refining 16

3.2 Associated Facilities

There is a number of other activities that need to be considered when calculating the NPI
emissions of substances for the site.

3.2.1 Fuel and Organic Liquid Storage

Storage for fuel and organic substances can occur at zinc processing sites. They are used
to hold substances such as LPG, diesel, petrol and oil for combustion purposes. Kerosene-
type organics may also be stored for solvent extraction operations, as well as small
quantities of organics used in the concentration process and for other operations. It is
unlikely that the sites will hold any significant quantities of other organic liquids.

Please refer to the EET Manual for Fuel and Organic Liquid Storage for further information.

3.2.2 Fossil Fuel Electric Power Generation

Fossil fuel electric power generation plants are delineated into steam plants, gas turbines,
co-generation and internal combustion engines. In relation to the zinc processing industry
it is likely that the only fossil fuel electric power generation system used would be the
internal combustion engines.

Internal combustion engines using petrol, natural gas, distillate and LPG coupled to
generators are commonly used to provide electricity in remote sites and in stand-by
(emergency) facilities.

The combustion of fossil fuel in power generation leads to the coincidental production of a
number of NPI Category 1 substances. Under the NPI, coincidental production is
considered use with regards to Category 1 threshold tests.

Please refer to the EET Manual for Fossil Fuel Electric Power Generation for further
information.

3.2.3 Combustion Engines

As mentioned previously, a frequent application of large stationary diesel engines is

electric power generation in remote areas and as a stand-by service. Mines and processing
facilities that have these engines need to consider their emissions during NPI calculations.

Please refer to the EET Manual for Combustion Engines for further information.

3.3 Maintenance Activities

Maintenance activities may require degreasing of metal components that lead to emissions
to air and water. Components of all wash down water streams need to be considered
when calculating emissions to water and land, as this effluent may contain metals, sulfuric
acid and descaling chemicals. Each zinc-processing site is required to investigate all the
chemicals used as part of maintenance activities to ensure that NPI reporting requirements
are met.

Zinc Concentrating, Smelting and Refining 17

4.0 Likely Emissions

Estimates of emissions of listed substances to air, water, and land shall be reported for
each substance that exceeds a defined threshold value of “usage” or emission. The
reporting list and detailed information on thresholds are contained in Section 4.1 and the
NPI Guide.

It is the responsibility of zinc concentrating, smelting and refining facilities to determine

which NPI substances are triggered for reporting. Table 4.1 indicates those NPI
substances likely to be of relevance where the threshold may be triggered by the zinc
concentrating, smelting and refining industry and the most appropriate method of
determining whether the threshold is triggered. This table is intended as a guide to
substances that may need to be reported for zinc concentrating, smelting and refining
facilities. A thorough inventory for each facility will provide a more accurate list.

The corresponding suggested methodology is only a guide, it is not an exclusive list, and
each facility will need to examine their current monitoring systems to identify which
method is the most appropriate.

Table 4.1 - NPI-Listed Substances Likely to Trigger Reporting, and Proposed Methods
for Determining Threshold Exceedance
SUBSTANCE TRIGGER TRIGGER METHOD
Ammonia (total) Usage 1 INV
Antimony & compounds Usage (Ore content) 1 DM, GF
Usage (Ore content) 1 DM, GF
Arsenic & compounds*
or power usage 2b C
Usage (Ore content) 1 DM, GF
Beryllium & compounds
or power usage 2b C
Boron & compounds Usage (Ore content) 1 DM, GF
Usage (Ore content) 1 DM, GF
Cadmium & compounds*
or power usage 2b C
Carbon disulfide Usage (Coincidental production) 1 DM, EC
Usage (Coincidental production) 1 DM, EC
Carbon monoxide*
Fuel use 2a DM, INV
Usage (Ore content) 1 DM, GF
Chromium (III) compounds
or power usage 2b C
Usage (Ore content) 1 DM, GF
Chromium (VI) compounds*
or power usage 2b C
Cobalt & compounds* Usage (Ore content) 1 DM, GF
Usage (Ore content) 1 DM, GF
Copper & compounds
or power usage 2b C
Cyanide (inorganic) compounds* Usage 1 INV

Zinc Concentrating, Smelting and Refining 18

Table 4.1 - NPI-Listed Substances Likely to Trigger Reporting, and Proposed Methods
for Determining Threshold Exceedance cont’
SUBSTANCE TRIGGER TRIGGER METHOD
Usage (Ore content) 1 DM, GF
Fluoride compounds*
or fuel use 2a INV
Usage (Usage & coincidental
1 INV, EC, DM
Hydrochloric acid production)
or fuel use 2a INV
Hydrogen sulfide Usage (Production on-site) 1 DM, EC
Usage (Ore content & anodes) 1 INV, DM, GF
Lead & compounds*
or power usage 2b C
Magnesium oxide fume Power usage 2b C
Manganese & compounds Usage (Ore content & catalyst) 1 DM, GF
Usage (Ore content) 1 DM, GF
Mercury & compounds*
or power usage 2b C
Usage (Ore content) 1 DM, GF
Nickel & compounds
or power usage 2b C
Usage (Coincidental production) 1 EC, DM
Nickel carbonyl
or power usage 2b C
Usage (Coincidental production) 1 EC, DM
Nickel subsulfide (matte)
or power usage 2b C
Oxides of nitrogen* Fuel use 2a DM, EC
Particulate matter ≤10µm* Fuel use 2a DM, EF
Polychlorinated dioxins & furans Power usage 2b C
Polycyclic aromatic
Fuel Use 2b DM, INV
hydrocarbons
Selenium & compounds Usage (ore content) 1 DM, GF
Fuel use 1 DM, EC
Sulfur dioxide*
or power usage 2b DM, EC
Sulfuric acid* Usage (coincidental production) 1 INV, EC
Total nitrogen* Discharge to surface waters 3 DM, EF
Total phosphorus* Discharge to surface waters 3 DM, EF
Total Volatile Organic Use or design bulk storage 1a C, INV
Compounds or fuel use 2a C, INV
Zinc & compounds Usage (ore content) 1 DM, GF
* Substances included in Table 1 of the NPI Guide.
** A number of methods may be used to determine threshold exceedance for NPI substances. The
method used will be related to the substance category and available information. Suggested methods that
may be used to calculate the emissions can be found in Tables 5.1 and 5.2.

Zinc Concentrating, Smelting and Refining 19

DM: Direct Measurement Å Direct measurement of NPI reportable emissions
in the stream (total N and P) or characterisation of
the ore body;
INV: Inventory Å Inventory or material usage (chemicals, fuel), with
NPI content of materials identified;
GF: Generic Factor Å Generic factor applies to default concentrations to
be used in the absence of facility-specific data;
EF: Emission Factor Å Emission factor to determine content in discharge
stream (eg. total N and P);
C: Capacity Å Capacity applies to the storage capacity of a
facility, maximum combustion rate, consumption
of energy or potential maximum power
consumption; and
EC: Engineering Å Engineering calculations may be used for a
Calculation number of substances such as sulfur dioxide.

NPI worksheets are available to assist facilities in determining substances that exceed
reporting triggers. These worksheets are included in Appendix B of the NPI Guide.

It is important to note that while the reporting threshold for a substance may not be
triggered during one reporting period, it may be triggered in another reporting period. As
such, it is important to review NPI reporting requirements each reporting period.

4.1 Reporting Thresholds

Thresholds have been set for five categories, although a substance may exceed thresholds
in more than one category (for example, copper may trigger reporting through its use
and/or the facility’s fuel usage). These are detailed below in simple terms. The NPI
reporting list and detailed information on thresholds are contained in The NPI Guide.

Within the zinc industry, trace metals within ore may trigger reporting thresholds, as may
the coincidental production of carbon disulfide from the decay of xanthates and the NPI
substance content of process chemicals used at facilities.

The usage of each of the substances listed as Category 1 and 1a under the NPI must be estimated to
determine whether the 10 tonnes (or 25 tonnes for VOCs) reporting threshold is exceeded. If the
threshold is exceeded, emissions of these Category 1 and 1a substances must be reported for all
operations/processes relating to the facility, even if the actual emissions of the substances are very
low or zero.

Ore will need to be characterised for all NPI metals and compounds to determine the
contribution of ore metal “use” to the total facility “use” of metals and compounds.

Direct measurement by representative sampling is the most accurate means of

characterising ore and hence determining “usage” of trace metals, as the metal content of
ore will vary between and within facilities. In the absence of facility-specific assays,

Zinc Concentrating, Smelting and Refining 20

generic ore assays may be used as the basis for reporting of metals “usage”. These assays
are presented in the EET Manual for Mining.

Where substances are “used” as a result of coincidental production, such as carbon

disulfide from the decay of xanthates, engineering calculations may be appropriate to
determine the amount that is “used” based on the chemical reaction rates.

Reference to facility inventories will facilitate the calculation of the mass of NPI substances
“used” through their presence in process chemicals. This approach will require recording
of the volumes of process chemicals used in a reporting period and determination of the
concentration of NPI substances in those chemicals. This data may be available from
material safety data sheets (MSDS) or directly from suppliers.

Table 4.2 below presents the concentrations within the ore that will trigger the reporting
threshold for Category 1 NPI substances.

Table 4.2 - NPI Triggers as Related to Metal Concentration in Ore

Metal conc. in ore Annual tonnage
(ppm) (millions of tonnes)
0.1 100
0.2 50
0.3 33.3
0.4 25
0.5 20
0.6 16.7
0.7 14.3
0.8 12.5
0.9 11.1
1 10
10 1
100 0.1

Total volatile organic compounds (VOCs) are considered under Category 1a. For more
information on the emission estimation of VOCs, please refer to the EET Manual for Fuel
and Organic Liquid Storage.

You should refer to the EET Manuals for Combustion Engines and Combustion in Boilers when
estimating emissions of substances that are products of combustion (ie. Category 2a and
2b substances).

Direct measurement (through representative sampling) of the total nitrogen and

phosphorus content of surface water discharges is likely to be the most appropriate means
of determining whether reporting thresholds are triggered.

Zinc Concentrating, Smelting and Refining 21

While the reporting threshold for Category 3 substances is unlikely to be exceeded at most
facilities, it is the responsibility of each facility to determine whether they exceed the
reporting threshold.

4.2 Reporting Requirements

Each facility is required to complete Worksheet 3 - Section B of the NPI Guide for each
substance triggered. This form requires the facility to specify the quantity of the substance
emitted (in kilograms per year) and distinguish the quantity emitted to air, water and
land. The worksheet also requires that the emission estimation technique be recorded.

Facilities have the option of differentiating between point source emissions and fugitive
emissions, as well as including a predicted release quantity for the next reporting year.

For a more detailed discussion on reporting thresholds and requirements facilities should
refer to the NPI Guide.

Zinc Concentrating, Smelting and Refining 22

5.0 Emission Estimation

5.1 Emission Estimation Techniques

Estimates of emissions of NPI-listed substances to air, water and land should be reported
for each substance that triggers a threshold. The reporting list and detailed information on
thresholds are contained in the NPI Guide at the front of this Handbook.

In general, there are four types of emission estimation techniques (EETs) that may be used
to estimate emissions from your facility.

The four types described in the NPI Guide are:

• Sampling or direct measurement;

• Mass balance;
• Fuel analysis or other engineering calculations; and
• Emission factors.

Select the EET, (or mix of EETs), that is most appropriate for your purposes. For example,
you might choose to use a mass balance to best estimate fugitive losses from pumps and
vents, direct measurement for stack and pipe emissions, and emission factors when
estimating losses from storage tanks and stockpiles.

If you estimate your emission by using any of these EETs, your data will be displayed on
the NPI database as being of ‘acceptable reliability’. Similarly, if your relevant
environmental authority has approved the use of EETs that are not outlined in this
manual, your data will also be displayed as being of ‘acceptable reliability’.

You are able to use emission estimation techniques that are not outlined in this
document. You must, however, seek the consent of your relevant environmental
authority. For example, if your company has developed site-specific emission factors,
you may use these if approved by your relevant environmental authority.

Those techniques available for estimating emissions of NPI substances from zinc
concentrating, smelting and refining activities are detailed in Table 5.1, while techniques
available for estimating emissions from ancillary activities and associated facilities at zinc
concentrating, smelting and refining sites are detailed in Table 5.2.

The estimation techniques detailed provide a range of options for facilities. These EETs
may be supplemented by other techniques to develop facility-specific EETs or to confirm
the accuracy of alternate EETs.

Zinc Concentrating, Smelting and Refining 23

While particular estimation methods are generally more suited to some applications, the
estimation method selected will be dependent on a number of factors, such as:

• Cost of estimation techniques;

• Ease of measurement or monitoring;
• Level or accuracy desired;
• Nature of the substance; and
• Existing monitoring and data availability.

This Manual seeks to provide the most effective emission estimation techniques for the
NPI substances relevant to this industry. However, the absence of an EET for a substance
in this handbook does not necessarily imply that an emission should not be reported to the
NPI. The obligation to report on all relevant emissions remains if reporting thresholds
have been exceeded.

You should note that the EETs presented in this manual relate principally to average
process emissions. Emissions resulting from non-routine events are rarely discussed in
the literature, and there is a general lack of EETs for such events. However, it is important
to recognise that emissions resulting from significant operating excursions and/or
accidental situations (eg. spills) will also need to be estimated. Emissions to land, air and
water from spills must be estimated and added to process emissions when calculating
total emissions for reporting purposes. The emission resulting from a spill is the net
emission, ie. the quantity of the NPI reportable substance spilled, less the quantity
recovered or consumed during clean up operations.

It should be appreciated that while the NPI requires reporting of metals and compounds,
such as copper and compounds, emissions relate only to the amount of metal emitted.

For example, if CuSO4 were emitted to the environment, only the Cu component would be
reportable. While CuSO4 has a molecular weight of 159 the Cu component has a molecular
weight of only 63. Reporting of the total CuSO4 emissions would therefore lead to an
emissions estimate about two and a half times greater than the actual emissions figure.

When estimating emissions it may be simpler to determine the percentage content of NPI
substances within distinct emission streams and report that percentage of the total
emission.

For example, the NPI requires that inorganic cyanide compounds only be reported. The
form in which cyanide is emitted should be factored into emission estimations where
practicable, although this may be very difficult to achieve where extensive cyanide
complexes are emitted. Where this is the case total cyanide emissions should be reported.

The NPI addresses the total loading of those forms of a substance required by the NPI to
the environment and does not distinguish between bioavailable and non-bioavailable
forms of a substance (except for total nitrogen and phosphorus emissions).

Zinc Concentrating, Smelting and Refining 24

For example, when considering metals such as cadmium and compounds, the total
loading of cadmium to the environment must be reported not just the bioavailable forms
of cadmium.

In reporting emissions it is important to note that while the reporting threshold for a
substance may be triggered this does not mean that the emissions will be necessarily of the
same magnitude. For example, most trace metals in the processed ore are likely to be
disposed of to the TSFs. However, only emissions from TSFs must be reported within the
NPI process.

The NPI has a commitment of not requiring any additional monitoring by facilities in
order to estimate their emissions. While monitoring is an EET available to facilities, a
range of EETs that does not require direct monitoring is available. However, in the
absence of monitoring data, a lower level of accuracy can be expected.

Appendix A details sources of data that may already be available to facilities. This data
may be used to assist in NPI reporting requirements.

A combination of these methods may be employed to estimate emissions to the

environment from particular process areas, such as emissions from TSFs.

The zinc concentrating, smelting and refining industry also requires a range of raw
material inputs that may be produced on-site at some facilities. Likewise some facilities
may produce additional products through their emission treatment processes, dependent
on the geochemistry of the ore. These are referred to in this manual as “Ancillary
Activities” and may include:

• Lead production;
• Copper production;
• Sulfuric acid production;
• Cadmium production;
• Selenium production; and
• Mercury production.

Where EET manuals have been produced to assist NPI reporting of these “Ancillary
Activities” they should be referred to in order to ensure that all substance usage and
emissions are fully accounted for. For example when sulfuric acid is used in the
production of fertilisers the appropriate EET manual should be referred to in order to
identify all emissions. Where manuals are not available, the use and emission of
substances should be accounted for as part of the facilities estimation methods detailed in
this handbook.

In all cases, when estimating emissions a facility should ensure that emissions are not
“double accounted” between different processes.

Tables 5.1 and 5.2 detail the NPI substance, the stage in the process where it is used and
emitted, and indicates appropriate emission estimation techniques. While emission factors
(EF) are identified as potential EETs for substances, emission factors may not currently be

Zinc Concentrating, Smelting and Refining 25

available for all substances. It is anticipated that emission factors will be developed for
these substances in the future.

The emission estimation techniques listed in Tables 5.1 and 5.2 are to be regarded as a
guide only, and each facility will need to investigate what sources of data they currently
have (refer to Appendix A of this document for potential data sources) and how they can
be applied. Similarly, the emission pathway (ie. to air, water, or land) listed for each
substance is the commonly expected pathway. However, it is possible that some facilities
may release some substances via an alternate pathway, which must be included when
reporting emissions. Thus each facility needs to refer to their individual flowsheets to
identify what their emissions are and how they are released.

Tables 5.1 and 5.2 have divided the facility into plant sections to aid in identifying where
possible emissions may occur. However, when a facility reports their emissions the
amount will be reported for the facility as a whole, for example a lead smelter will report
only one value for SO2, which is the summation of all the individual SO2 and fugitive
emissions across the entire facility.

Zinc Concentrating, Smelting and Refining 26

Table 5.1 - Techniques Available for Estimating Emissions of NPI Substances from Zinc Concentrating, Smelting and Refining
Activities
Concentrating Smelting Electrolytic Process Emissions From
Substances
Grinding Flotation Thickening Sintering ISF Blast Refinery Roasting Leaching Purification Electrolysis/ Slag TSFs
& Filtering Furnace Casting landfill
A W,L
Ammonia
MB MB
A A A A A A L A W,L
Antimony
MB MB MB MB MB MB DM,EF MB MB
A A A A A A A W,L
Arsenic
MB DM DM DM DM MB MB DM
Beryllium A A A A A A A W,L
compounds MB DM DM DM DM MB MB MB
Boron & A A A A A A A W,L
compounds MB DM DM DM DM MB MB MB
Cadmium & A A A A A A A W,L
compounds MB DM DM DM DM MB MB DM
A W,L
Carbon disulfide
EC MB
A A A A
Carbon monoxide
DM DM DM DM
Chromium (III) & A A A A A A A W,L
compounds MB MB MB MB MB MB MB MB
Chromium (VI) & A A A A A A A W,L
compounds MB MB MB MB MB MB MB MB
A A A A A A W,L
Cobalt
MB MB MB MB MB MB MB
Copper & A A A A A A A W,L
compounds MB MB MB MB MB MB MB MB

Zinc Concentrating, Smelting and Refining 27

Table 5.1 - Techniques Available for Estimating Emissions of NPI Substances from Zinc Concentrating, Smelting and Refining
Activities cont’
Concentrating Smelting Electrolytic Process Emissions From
Substances
Grinding Flotation Thickening Sintering ISF Blast Refinery Roasting Leaching Purification Electrolysis/ Slag TSFs
& Filtering Furnace Casting landfill
A A A A A A A W,L
Cyanide
MB MB MB MB MB MB MB MB
Fluoride W,L
compounds MB
W A A A A A,W A,W W,L
Hydrochloric Acid
EC DM DM DM DM MB D/M MB
A A
Hydrogen sulfide
DM DM
A A A A A A A W,L
Lead & compounds
MB DM DM DM DM MB MB DM
Manganese Oxide A A A A A
Fume DM DM DM DM DM
Manganese & A A A A A A A W,L
compounds MB MB MB MB MB MB MB MB
Mercury & A A A A A A A W,L
compounds MB DM DM DM DM MB MB DM
Nickel & A A A A A A A W,L
compounds MB DM DM DM DM DM DM DM

Nickel carbonyl

A A A A A A A W,L
Nickel Subsulfide
MB MB MB MB MB MB MB MB

Zinc Concentrating, Smelting and Refining 28

Table 5.1 - Techniques Available for Estimating Emissions of NPI Substances from Zinc Concentrating, Smelting and Refining
Activities cont’
Concentrating Smelting Electrolytic Process Emissions From
Substances Thickening ISF Blast Electrolysis/ Slag
Grinding Flotation Sintering Refinery Roasting Leaching Purification TSFs
& Filtering Furnace Casting landfil

Organo-tin W,L
compounds MB
A A A A
Oxides of Nitrogen
EC EC EC EC
Particulate matter A A A A A A A
≤10µm EF EF EF EF EF EF EF
Polychlorinated A A A A A A
dioxins & furans DM DM DM DM DM DM
Selenium & A A A A A A A W,L
compounds MB DM DM DM DM MB MB DM
A A A A
Sulfur dioxide *
DM DM DM EF, DM
L,W W
Sulfuric acid
MB DM
W
Total Nitrogen
EC
W,L
Total Phosphorus
EC
A A A A A A A W,L
Zinc & compounds
M/B DM DM DM DM MB MB DM
*
Notes: DM Direct Measurement A Emission to Air emission factor for fugitives,
MB Mass Balance W Emission to Water direct measurement for process situation
EC Engineering Calculations L Emission to Land
EF Emission Factor

Zinc Concentrating, Smelting and Refining 29

Table 5.2 - Techniques Available for Estimating Emissions of NPI Substances from Ancillary Activities and Associated Activities
Related to Zinc Processing
Cadmium Selenium Plant Mercury Fossil Fuel Electric Fuel & Organic Combustion Waste Water
Substance Acid Plant Generation
Plant Plant Liquid Storage Engines Treatment Plant
A
Ammonia
DM
A A A A W
Antimony
MB MB MB MB DM, MB
A A A A W
Arsenic
MB MB MB MB DM, MB
Beryllium & A A A A
compounds MB MB MB MB
Boron & A A A A
compounds MB MB MB MB
Cadmium & W A W
compounds DM MB DM, MB
A A
Carbon monoxide
MB MB
Chromium (III) & A A W
compounds MB MB DM, MB
Chromium (VI) & A A W
compounds MB MB DM, MB
Cobalt & A A A A W
compounds MB MB MB MB DM, MB
Copper & A A A W
compounds MB MB MB DM, MB

Cyanide

Zinc Concentrating, Smelting and Refining 30

Table 5.2 - Techniques Available for Estimating Emissions of NPI Substances from Ancillary Activities and Associated Activities
Related to Zinc Processing cont’
Cadmium Selenium Plant Mercury Fossil Fuel Electric Fuel & Organic Combustion Waste Water
Substance Acid Plant Generation
Plant Plant Liquid Storage Engines Treatment Plant
W
Fluoride
DM, MB
A A,
Hydrogen Sulfide
MB EF
Lead & A,W A A W
compounds MB,DM MB MB DM, MB
Manganese & A A A W
compounds MB MB MB D/M, M/B
Mercury & A A,W W,L A A W
compounds MB MB,DM EF,DM MB MB DM, MB
W
Nickel carbonyl
DM, MB

Nickel subsulfide

Organo-tin
compounds
Oxides of A A
nitrogen MB MB
Particulate matter A A A A
≤10µm MB MB MB MB
Polycyclic A A A
aromatic DM DM DM
hydrocarbons
Selenium & A,W A A W
compounds DM MB MB DM, MB

Zinc Concentrating, Smelting and Refining 31

Table 5.2 - Techniques Available for Estimating Emissions of NPI Substances from Ancillary Activities and Associated Activities
Related to Zinc Processing cont’
Cadmium Selenium Plant Mercury Fossil Fuel Electric Fuel & Organic Combustion Waste Water
Substance Acid Plant Generation
Plant Plant Liquid Storage Engines Treatment Plant
A A A
Sulfur dioxide
DM MB EF
A,W A,W A,W A,W
Sulfuric acid
MB MB MB MB
W
Total nitrogen
DM, EB
W
Total phosphorus
DM, EB
A A A
Total VOCs
EF EF EF
Zinc & A,W A,W A A W
compounds MB,DM MB,DM MB MB DM, MB
Notes: DM Direct Measurement A Emission to Air
MB Mass Balance W Emission to Water
EC Engineering Calculations L Emission to Land
EF Emission Factor

Zinc Concentrating, Smelting and Refining 32

5.1.1 Direct Measurement

While not a requirement of the NPI, direct measurement (or source monitoring) is one of
the more accurate methods of estimating emissions of substances from processes and
facilities.

Facilities may decide to undertake direct measurement in order to:

• More accurately estimate their emissions of particular NPI substances;

• Verify estimates from alternative EETs;
• Develop site-specific emission factors; or
• Provide supporting data for other EETs.

Source measurement programs should be designed to be representative of the parameters

being considered, taking standard and non-standard conditions into account.
Additionally, the immediate and long-term aim of the measurement program should be
decided in order to avoid unnecessary ongoing monitoring.

Facilities may have existing source monitoring commitments and data that can be applied
to the reporting requirements of the NPI. See Appendix A.

Facilities may also have the analytical expertise on-site to enable the source monitoring
and analysis of NPI substances to be undertaken in a more cost-effective manner.

Direct measurement data may be used to calculate actual loads to the environment by
multiplying the concentration of the NPI substances in the final emission stream, by the
mass of the final emission stream.

Equation 5.1
Ei = Ci * V * [273 / (273 + T)]
where:

Ei = hourly emissions of pollutant i (kg/hr)

Ci = concentration of pollutant i (kg/m3)
V = stack gas volumetric flow rate (m3/hr)
T = gas temperature (°C)
273 = 273 K (0°C)

Where direct measurement is undertaken, it is essential that sampling and source

monitoring procedures are established. The procedures should ensure that all sampling
and analyses are undertaken in a standard manner and in compliance with Australian or
other relevant standards.

Zinc Concentrating, Smelting and Refining 33

5.1.2 Engineering Calculations

Engineering calculations may be used to estimate emissions from processes subject to rigid
controls, such as where a substance is formed coincidentally, such as carbon disulfide,
where the substance breaks down very quickly in the atmosphere, or where its fate is well
understood from process chemistry and operations.

These processes may be designed to operate at a given efficiency, and while variations will
occur it may be valid to assume a given performance efficiency under normal operating
conditions.

Engineering calculations may utilise standard physical and chemical laws and constants to
allow the estimation of particular emissions. These may include equilibrium constants,
thermodynamic properties of processes, chemical reactions, pressure constants, and
physical laws such as Boyle’s Law.

Engineering calculations are based on known performance standards of particular

processes and equipment, physical/chemical properties (such as vapour pressure) of the
substance and mathematical relationships (such as ideal gas law).

Modelling, an advanced form of an engineering calculation, may be utilised to determine

the fate of substances emitted to the environment, including emissions to air and
groundwater.

For cyanide and dissolved metal emissions from TSFs, modelling would be likely to have
at least two components:

• The fate of the substance within the TSF; and

• The fate and transport of substances within groundwater.

Models may be very simple, based on minimal data and making broad based
assumptions, or complex with factors for weather influences, chemical speciation and site-
specific factors.

The complexity of a model will influence the accuracy of any emission estimations made
using this method. Wherever possible, however, models should be verified by direct
measurement under a range of conditions. With effective model verification, models may
be factored to allow for site-specific influences, and significant influences may be included
within the model itself.

5.1.3 Mass Balance

Mass balances provide an estimate of emissions where known quantities of substances are
supplied to a process, and the process fate of the substance is both known and
quantifiable.

It is essential that the mass balance calculations address all losses and fates of a substance
and utilise the best available data.

As a result of inherent errors in the estimation of inputs to and losses from a facility or
process, and the fates of those substances, the effectiveness of a mass balance approach in
estimating minor emissions may be questionable and may contain broad error bands.

Zinc Concentrating, Smelting and Refining 34

Chemical Usage

The emission of chemicals from some sources (either as a result of normal operations,
spillage or incidents) may be estimated through mass balance.

Process and domestic-type chemicals used within the facility may be emitted to the
environment. The full inventory of these chemicals used within a reporting period may be
assumed to be either emitted to the environment or transferred to an alternative disposal,
recycling or reuse facility.

In order to estimate the fate of chemicals, and their component NPI substances, the
following approach should be taken:

• Mass of NPI substances within chemicals determined (including coincidental

production);
• Inventory (or hazardous substances registers) of chemical usage maintained; and
• Fate of chemical determined:
• Is chemical emitted to the environment or transferred?
• Is chemical treated prior to emission from the facility?
• Is chemical emitted to air, water or land?
• Does chemical undergo partitioning into other forms?
• What are the fates of partitioned substances?

This approach may be applied to chemical usage in areas such as:

• Chemical storage areas;

• Laboratories;
• Workshops;
• Kitchens;
• Domestic-type activities; and
• Washdown areas.

Effluent Streams

Where a facility uses a listed mineral acid or base, with this acid or base being effectively
neutralised in use or during wastewater treatment (to a pH of 6 to 8, as required by most
State and Territory effluent standards), no emission quantities should be reported. If the
acid or base is itself transformed into another listed substance, however, the quantity of
this substance coincidentally produced must be determined to assess if a threshold value
has been reached. For example, sulfuric acid, which is itself a listed substance, often yields
hydrogen sulfide in effluent streams, and requires reporting where annual emissions total
10 tonnes or more.

Zinc Concentrating, Smelting and Refining 35

Wastewater treatment may precipitate the reportable chemical in a sludge. Facilities are
often required to obtain data on the concentration of metals or other substances in sludges
as part of their licensing requirement and this data can be used to calculate the emissions
as kilograms of sludge multiplied by the concentrations of the substance in the sludge.
Although listed substances in sludges transferred off-site do not require reporting,
determining this loss can assist with determining other process losses or may require
reporting if the sludge is disposed of on-site.

For many chemicals used and emitted during chemical processes, some degradation in
treatment may occur so that the entire chemical is not transferred to the sludge. Facilities
can estimate the amount of reportable compounds in the sludge by using measured data,
or by subtracting the amount biodegraded from the total amount removed in treatment.
The amount of removal can be determined from operating data, and the extent of
biodegradation might be obtained from published studies. If the biodegradability of the
chemical cannot be measured or is not known, reporting facilities should assume that all
removal is due to absorption to sludge.

5.1.4 Emission Factors

Background

An emission factor (EF) is a tool that is used to estimate emissions to the environment, and
may be either formulae or values that are derived from similar operations. Emission
factors are a useful tool for estimating emissions where the relationship between the
emission and the “use” of substances is well defined. They are widely used in estimating
emissions from combustion sources, such as in furnaces and in fuel usage generally.

In this manual, an EF relates to the quantity of substances emitted from a source to some
common activity associated with those emissions. Emission factors are obtained from
United States (US), European and Australian sources. They are usually expressed as the
weight of the substance emitted multiplied by the unit weight, volume, distance or
duration of the activity emitting the substance, such as the mass of PM10 and TSP produced
per tonne of ore handled.

Emission factors are used to estimate a facility’s emissions by the following equation:

Equation 5.2
Ei = A * EFi * [1 - CEi/100]
where:

Ei = hourly emissions of pollutant i (kg/hr)

A = activity rate (t/hr)
EFi = uncontrolled emission factor for pollutant i (kg/t)
CEi = overall control efficiency for pollutant i (%)

Zinc Concentrating, Smelting and Refining 36

Some emission factors may involve the use of more complex equations and require
differentiation of substance fates. Estimation of cyanide fates is an example of a substance
that may require the use of more complex EETs.

Emission factors are derived from direct measurement of actual emission loads from a
range of similar plants or equipment. While emission factors have an empirical basis they
are based on standard equipment and operating practices. As such, the site-specific
characteristics of facilities will introduce inaccuracies to the use of emission factors, and
with the increasing use of improved technologies and control methods, emission factors
may become dated.

Emission factors may be verified at individual facilities by carrying out direct monitoring
of emission sources and developing site-specific variations to the standard factors to
reflect on-site operational processes and practices.

5.2 Acceptable Reliability and Uncertainty

This section is intended to give a general overview of some of the inaccuracies associated
with each of the techniques. Although the NPI does not favour one emission estimation
technique over another, this section does attempt to evaluate the available emission
estimation techniques with regards to accuracy.

Several techniques are available for calculating emissions from zinc facilities. The
technique chosen is dependent on available data, and available resources, and the degree
of accuracy sought by the facility in undertaking the estimate. In general, site-specific data
that is representative of normal operations is more accurate than industry-averaged data,
such as emission factors.

5.2.1 Direct Measurement

Use of stack and/or workplace health and safety sampling data is likely to be a relatively
accurate method of estimating air emissions from lead concentrating, smelting and
refining facilities. However, collection and analysis of samples from facilities can be very
expensive and especially complicated where a variety of NPI-listed substances are
emitted, and where most of these emissions are fugitive in nature. Sampling data from a
specific process may not be representative of the entire manufacturing operation, and may
provide only one example of the facility’s emissions.

To be representative, sampling data used for NPI reporting purposes needs to be collected
over a period of time, and to cover all aspects of production.

5.2.2 Mass Balance

Calculating emissions using a mass balance appears to be a straightforward approach to

emission estimation. However, it is likely that few Australian zinc facilities consistently
track material usage and waste generation with the overall accuracy needed for
application of this method. Inaccuracies associated with individual material tracking, or

Zinc Concentrating, Smelting and Refining 37

other activities inherent in each material handling stage, can result in large deviations for
total facility emissions. Because emissions from specific materials are typically below 2
percent of gross consumption, an error of only ± 5 percent in any one step of the operation
can significantly skew emission estimations.

5.2.3 Engineering Calculations

Theoretical and complex equations, or models, can be used for estimating emissions. EET
equations are available for the following types of emissions common to zinc concentrating
and smelting/refining facilities.

Use of emission equations to estimate emissions is a more complex and time-consuming

process than the use of emission factors. Emission equations require more detailed inputs
than the use of emission factors but they do provide an emission estimate that is based on
facility-specific conditions

5.2.4 Emission Factors

Emission Factor Rating

Every emission factor has an associated emission factor rating (EFR) code. This rating
system is common to EETs for all industries and sectors and therefore, to all Industry
Handbooks. They are based on rating systems developed by the United States
Environmental Protection Agency (US EPA), and by the European Environment Agency
(EEA). Consequently, the ratings may not be directly relevant to Australian industry.
Sources for all emission factors cited can be found in the reference section of this
document. The emission factor ratings will not form part of the public NPI database.

When using emission factors, you should be aware of the associated EFR code and what
that rating implies. An A or B rating indicates a greater degree of certainty than a D or E
rating. The less certainty, the more likely that a given emission factor for a specific source
or category is not representative of the source type. These ratings notwithstanding, the
main criterion affecting the uncertainty of an emission factor remains the degree of
similarity between the equipment/process selected in applying the factor, and the target
equipment/process from which the factor was derived.

The EFR system is as follows:

A - Excellent
B - Above Average
C - Average
D - Below Average
E - Poor
U - Unrated

Zinc Concentrating, Smelting and Refining 38

Estimating your facility’s emissions based on emission factors only, and without taking
into account any control measures, may have an uncertainty as high as 100%.

Where emission factor ratings have not been included, these emission factors should be
assumed to have a rating of “U” or unrated factors. This rating reflects the limited amount
of research and data upon which the factors have been based, and/or the confidence
associated with the factor itself.

5.3 NPI Reporting Steps

Step 1

Identify all substances and materials used and/or produced through production processes
on your site each year.

Step 2

Determine what substances identified in Step 1 are also listed in Table 1: NPI Substances,
found in Appendix A of the NPI Guide. Substances that are likely to be used at zinc
processing and associated facilities are listed in Table 4.1.

The substances that match are required to be reported to the NPI, if the threshold for
reporting is met.

Step 3

Determine quantities used on-site for those substances identified in Step 2, as well as the
amount of energy and fuel consumed

Step 4

Compare the quantities used for the substances against the thresholds.

If your facility triggers a threshold for a substance or substances, you are required to
report emissions of that substance to the NPI.

Step 5

Calculate the emissions for each substance from both fugitive and point sources. Refer to
Table 5.1 and Table 5.2, which present recommended techniques available for estimating
emissions from various sources.

Refer to Sections 6, 7 and 8 of this manual, which provide examples of the various
estimation techniques used to calculate emissions to air, water and land.

Zinc Concentrating, Smelting and Refining 39

6.0 Emissions to Air

6.1 Background

Significant emissions to air within the zinc concentrating, smelting and refining industry
will be related to:

• Stack emissions from smelters;

• The stockpiling, movement and comminution of ore;
• The operation of process plants including electrolytic processing; and
• The operation of tailing storage facilities.

Emissions to air are estimated from their point of creation rather than at the facility
boundary. Emissions estimation does not take into account the fate of emitted substances,
such as the speed of their subsequent decay within the atmosphere.

Air emissions may be categorised as:

• Fugitive emissions; and

• Point Source emissions.

Fugitive Emissions
These are emissions that are not released through a vent or stack. Examples of fugitive
emissions include dust from stockpiles, volatilisation of vapour from vats or open vessels,
and dust arising during material handling. Emissions emanating from ridgeline roof-
vents, louvres, and open doors of a building as well as equipment leaks from valves and
flanges are also examples of fugitive emissions.

Emission factor EETs are the usual method for determining losses through fugitive
emissions, however in the absence of suitable emission factors alternate EETs will need to
be applied. These may include engineering calculations, such as modelling PM10 from
stockpiles, or a facility developed EET. As discussed previously in Section 5.0, you may
estimate your emissions by using the EETs presented in this manual and your data will be
included in the NPI database as being of “acceptable reliability”. Or if your relevant
environmental authority has approved the use of emission estimation techniques that are
not outlined in this manual your data will also be displayed as being of “acceptable
reliability”.

Point Source Emissions

These emissions are exhausted into a vent (excluding roof vents) or stack and emitted
through a single point source into the atmosphere. An air emissions control device such as
a carbon adsorption unit, scrubber, fabric filter, or afterburner may “treat” stack emissions
prior to their release, reducing their total loading to the atmosphere.

Zinc Concentrating, Smelting and Refining 40

6.2 Converter and Smelter Emissions

Emissions from primary zinc smelters are principally particulate matter and oxides of
sulfur. Emissions are generated primarily from the smelting furnaces and converters.
Fugitive emissions are generated during material handling operations. Zinc and lead
oxides or sulfides are significant constituents of the particulate matter, but other metals
such as arsenic, antimony, cadmium, and mercury may also be present, along with
metallic sulfates and sulfuric acid mist. Significant emissions of SO2 occur from various
processes associated with primary zinc smelting of sulfide ores. Recovery of this SO2, for
production of sulfuric acid is good environmental; practice, and may be economically
beneficial. Fuel combustion products also contribute to emissions from smelting furnaces.

6.2.1 Direct Measurement

Direct measurement (or source monitoring) is one of the more accurate methods of
estimating air emissions from smelters/converters. Source monitoring programs for air
emissions such as SO2 or airborne metal particulates are often part of the licensing
requirements for the smelter complex. A discussion on the application of this technique to
SO2 emissions can be found in Section 9.

6.2.2 Mass Balance

Emissions (such as sulfur dioxide and metals) from smelter and refining operations may
be estimated through the use of a mass balance. However, some direct sampling may be
desirable to improve components of the mass balance eg. sulfur/metals content of process
inputs and outputs.

It is important that the fates of component substances are considered within the mass
balance and that all assumptions are stated. For example, it may be assumed that all
sulfur is converted to sulfur dioxide during combustion, and slag content analyses may
suggest that a percentage of some metals are emitted.

The mass balance approach allows fugitive and other emissions to the environment to be
estimated. Figure 6.1 shows a typical “box” approach to mass balances.

Air Emissions
(fugitives, stacks)

Smelter /
Feedstock & Fuel Product
Converter

Solid Waste

Figure 6.1 - Emissions Estimation for Converter and Smelter Operations

Zinc Concentrating, Smelting and Refining 41

Air emissions may be estimated where the NPI substance concentrations of the feedstock,
product and solid wastes have been effectively characterised.

Sulfur dioxide (SO2) emissions from converter and smelter operations may be estimated
through the use of mass balance. However, direct monitoring will be required for some
aspects of the mass balance, such as sulfur content of process inputs and outputs.

The approach detailed below allows for fugitive and other emissions to the environment
to be accounted for, and the verification of on-line monitoring and mass balance findings.

Where data is not available estimates may be used and any shortfalls assumed to be losses
to the environment.

While there are many variables in the mass balance, the errors inherent to the mass
balance approach may be minimised through continued development and refinement of
the mass balance equation, as displayed through the addition of more variables in
Figure 6.2.

Flux (A2)
Concentrate (A1) Fuel (A3)

Smelter Off-
gases Slag (B)
Smelter and
Refining
Process Other waste gases
Acid Plant (C)

H2 SO4 Acid Plant Product

product Gases (F)
(E) (D)

Figure 6.2 - Refined Mass Balance Model

Where: Inputs = Estimated outputs + Assumed outputs

For example: A1 + A2 + A3 = (B + C + D) + (E + F) + Fugitives

6.3 Dust and PM10

6.3.1 Direct Measurement

PM10 emissions are estimated from their point of creation. As such, the presence of a
buffer zone will not influence the estimated emissions.

Direct measurement may be designed to monitor overall site emissions or emissions from
particular processes. In all cases it will be important to ensure background levels are
considered and factored into emission estimations.

Zinc Concentrating, Smelting and Refining 42

Total suspended particulates (TSP) are also referred to as total particulate matter
(total PM). To determine PM10 from total PM emissions, a size analysis may need to be
undertaken. The weight of the PM10 fraction can then be multiplied by the total PM
emission rate to produce PM10 emissions. Alternatively, assume that 100% of PM emissions
are PM10, ie. assume that all particulate matter emitted to air has an equivalent
aerodynamic diameter of 10 micrometres or less ie. ≤10µm.

6.3.2 Emission Factors

Processing Areas

The EET Manual for Mining provides emission factors for PM10 and TSP sources within the
processing area. It should be noted that TSP is not a reporting requirement under the NPI,
but may be used to estimate metals content of emitted dust only.

Metal emissions can be estimated as a fraction of the TSP emissions, based on available
assay data. Where assay data and facility-specific information are not available for metals
in dust emissions the concentrations in Table B2 of the EET Manual for Mining should be
used as a default to estimate metal emissions.

Tailing Storage Facilities (TSFs)

Dust emissions from TSFs should only be calculated from those TSFs with the potential to
result in dust emissions.

A range of factors influence the dust generation from TSFs, including:

• Moisture content;
• Salt concentration;
• Vegetation cover and organic matter (lichens, moss etc.);
• Surface structure (structural & textural cracks & inhomogenity);
• Traffic (mechanical and animals); and
• Weathering (Source: Carras, 1998).

Retaining a wet surface on TSFs will prevent dust generation (BPEMIM, Tailings
Containment, 1995), while TSFs with a low salt content (and low moisture content) have a
greater potential for dust generation than TSFs with a high salt content. Revegetation of
decommissioned TSFs will minimise their potential for dust generation.

The potential for TSFs to generate dust should be assessed on a facility basis. The
assessment should be based on known factors that influence dust generation and
observational/monitored results.

In the absence of facility-specific information the following assumptions may be made:

• Zero dust generation from TSFs where hyper-saline water used in process;
• Zero dust generation from “wet” area of TSFs; and
• Zero dust generation from vegetated TSFs.

Zinc Concentrating, Smelting and Refining 43

Smelting Facility

Particulate emission factors were extracted from the US EPA AP-42 document,
Section 12.7, Zinc Smelting (1999).

Controlled and uncontrolled particulate emission factors for points within a zinc smelting
facility are presented in Table 6.1. Fugitive emission factors are presented in Table 6.2.

These emission factors should be applied carefully. Emission factors for sintering
operations are derived from data from a single facility no longer operating. Others are
estimated based on similar operations in the steel, lead, and copper industries
(US EPA, 1999).

Table 6.1 - Particulate Emission Factors for Zinc Smeltinga

Emission Emission
Process Uncontrolled Factor Controlled Factor
Rating Rating
Roasting
Multiple hearthb (SCC 3-03-030-02) 113 E ND NA
c
Suspension (SCC 3-03-030-07) 1000 E 4 E
d
Fluidized bed (SCC 3-03-030-08) 1083 E ND NA
Sinter plant (SCC 3-03-030-03)
Uncontrollede 62.5 E NA NA
f
With cyclone NA NA 24.1 E
f
With cyclone and ESP NA NA 8.25 E
g
Verticle retort (SCC 3-03-030-29) 7.15 D ND NA
h
Electric retort (SCC 3-03-030-29 10.0 E ND NA
j
Electrolytic process (SCC 3-03-030-
3.3 E ND NA
06)
Source: (AP- 42 US EPA, 1999)
a
Factors are for kg/t of zinc ore processed. SCC = Source Classification Code.
ESP = Electrostatic precipitator. ND = no data. NA= not applicable
b
References 14,11,19. Averaged from an estimated 10% of feed released as particulate, zinc production
rate at 60% of roaster feed rate, and other estimates.
c
References 14,11,19. Based on an average of 60% of feed released as particulate emission and a zinc
production rate at 60% of roaster feed rate. Controlled emissions based on 20% dropout in waste heat
boiler and 99.5% dropout and ESP.
d
References 1, 3. Based on an average 65% of feed released as particulate emissions and a zinc production
rate of 60% of roaster feed rate.
e
Reference 14. Based on unspecified industrial source data.
f
Reference 17. Data not necessarily compatible with uncontrolled emissions.
g
Reference 17.
h
Reference 13. Based on unspecified industrial source data.
j
Reference 1

Zinc Concentrating, Smelting and Refining 44

Table 6.2 - Uncontrolled Fugitive Particulate Emission Factors for Slab Zinc Smeltinga
Process Emissions Emission Factor
Rating

Roasting (SCC 3-03-030-24) Negligible NS

b
Sinter plant
Wind box (SCC 3-03-030-27) 0.12 - 0.55 E
Discharge screens (SCC 3-03-030-26) 0.28 - 1.22 E
c
Retort building (SCC 3-03-030-27) 1.0 - 2.0 E
d
Casting (SCC 3-03-030-28) 1.26 E
Source: (AP - 42 US EPA, 1999)
a
Reference 20. Factors are in kg/t of product. SCC = Source Classification Code.
NA = Not applicable.
b
From steel industry operations for which there are emission factors. Based on quantity of sinter
produced.
c
From lead industry operations.
d
From copper industry operations.

6.4 Metals in Dust

6.4.1 Direct Measurement

PM10 and TSP emissions may contain a metal fraction. This metal fraction may be
estimated from available ore assays, however, speciation of PM10 and TSP samples by
direct analysis will allow estimation of the facility’s emissions of these metals. Periodic
analysis of dust samples will allow the proportion of dust to be determined with further
level of accuracy.

It is important to note that reporting of metals may be triggered by a number of categories

but all triggered substances must be estimated from all sources for reporting purposes.

6.4.2 Emission Factors

PM10 and TSP may contain a metal fraction, which will represent part of the facility’s
metals emissions.

These emissions may be estimated, using an emission factor approach from:

• Metal content of ore (generic or facility-specific); and

• Dust generation estimates (either through emission factors, modelling or direct
monitoring).

The metal’s fraction for all processing dust sources may be assumed to be the same as that
for unprocessed ore, in the absence of more suitable data. Fractions may be sourced from
facility-specific assays or generic ore types (Appendix A). However, greater accuracy may
be obtained by direct analysis of PM10 and TSP filter samples in order to determine the
speciation of the dust.

Zinc Concentrating, Smelting and Refining 45

The metal content (including cyanide) of TSF dust emissions should be based on
representative sampling of the TSFs surface matrix.

6.5 Acid Mist

An increasingly important alternative to conventional zinc smelting and refining is
electrowinning technology, in which dilute sulfuric acid is percolated through zinc calcine
dust to leach out the zinc. The zinc is recovered by plating onto a starter cathode in a
process called electrowinning.

The leaching/electrowinning process is an alternative to smelting but it and its

corresponding emission streams are fundamentally different from smelting.

The main emissions to air are leach solution mist from the leaching process and electrolyte
mist from the electrowinning process. Both contain sulfuric acid.

6.5.1 Direct Measurement

Little direct measurement is possible in an open environment, however some sites do

measure airborne sulfuric acid. Others rely on contouring of the plant’s immediate
landscape to drain rainfall into the dam or mine pits. This reclaims spray, mist and dust
back to the site. This suggests that the process and plant is a relatively closed cycle
operation where rainfall washes many emissions back to the plant for re-integration into
the process cycle.

6.5.2 Mass Balance

Emissions from leaching/electrowinning operations may be estimated through the use of

mass balance. Direct measurement of the process inputs is undertaken, in order to
minimise losses (outputs) which need to be replaced to keep the process running. The
process fate of the acid mist may be estimated from the additional acid input that is
required over time.

6.5.3 Engineering Calculations

Engineering calculations may be used to estimate acid mist emissions from the overall
process. The process is designed to operate at a certain level of efficiency, and while
variations will occur it may be valid to assume a given performance efficiency under
normal operating conditions.

The calculations may utilise the chemical reactions that occur in the leaching and
electrowinning processes. In simple terms these would be as follows:

ZnO + H2SO4 → ZnSO4 + H2O ↔ Zn + SO4

2+ 2-
Leach:

Electrowinning: Zn2+ + 2e– → Zn

Zinc Concentrating, Smelting and Refining 46

6.6 Emissions from Associated Facilities and Ancillary Activities

Associated facilities at zinc smelters and refineries can also produce NPI reportable
emissions. Please refer to the EET Manuals mentioned below for further guidance on
estimating emissions from these ancillary activities.

6.6.1 Emission Estimation for Fuel

Fuel analysis is an example of an engineering calculation and can be used to predict SO2,
metals, and other emissions based on the application of conservation laws, if fuel rate is
measured. The presence of certain elements in fuels may be used to predict their presence
in emission streams. This includes elements such as sulfur that may be converted into
other compounds during the combustion process.

SO2 emissions from combustion can be calculated based on the concentration of sulfur in
fuel. Equation 6.1 can be used in fuel analysis emission calculations.

This approach assumes complete (100%) conversion of sulfur to SO2. Therefore, for every
kilogram of sulfur (EW = 32) burned, two kilograms of SO2 (MW = 64) are emitted.

Equation 6.1

Ekpy,SO2 = Qf * Ci/100 *
MW SO 2
* OpHrs
EWS

where:
Ekpy,SO2 = amount of SO2 emitted (kg/yr)
Qf = fuel use (kg/hr)
Ci = pollutant concentration of fuel weight percent %
MWSO 2 = molecular weight of SO2 (= 64) (kg/kg-mole)
EWS = elemental weight of S (= 32) (kg/kg-mole)
OpHrs = operating hours (hr/yr)

Zinc Concentrating, Smelting and Refining 47

Example 6.1 illustrates the use of Equation 6.1.

Example 6.1 - Using Fuel Analysis Data

Ekpy,SO2 may be calculated using Equation 6.1 and given the following:

Qf = 20 900 kg/hr
Weight percent sulfur in fuel = 1.17%
Operating hours = 1500 hr/yr

Ekpy,SO2 = Qf * Ci/100 *
MW SO 2
* OpHrs
EW S

1.17  64 
= 20 900 * *   *1500
100  32 
= 733 590 kg/yr

Therefore, under these operating conditions the amount of SO2 emitted to the air is
733 590 kg per year.

Guidance on emissions from fuel combustion may also be found in the following NPI
manuals:

• EET Manual for Fossil Fuel Electric Power Generation;

• EET Manual for Combustion Engines; and
• EET Manual for Combustion in Boilers.

6.6.2 Air Emissions from Fuel and Organic Liquid Storage

Estimation of emissions from storage vessels containing fuel and organic liquids is
required by the NPI. Please refer to the EET Manual for Fuel and Organic Liquid Storage for
further information.
6.6.3 Air Emissions from Fossil Fuel Electric Power Generation

The EET Manual for Fossil Fuel Electric Power Generation describes the procedures and
recommended approaches for estimating emissions from facilities engaged in fossil fuel
electric power generation. The manual considers combustion and non-combustion
sources of emissions to air, water and land.

A fossil fuel electricity generation plant is delineated into five (5) categories - the only
category applicable to the zinc processing sites is the internal combustion engine,
commonly used for small remote sites or stand-by (emergency) generation. Therefore,
emission estimations will relate to internal combustion (stationary) engines.

Zinc Concentrating, Smelting and Refining 48

6.6.4 Emissions from Internal Combustion (Stationary) Engines

The EET Manual for Combustion Engines contains emission factors and emission estimation
techniques that can be used as guidance on estimating emissions from internal combustion
engines.

6.6.5 Maintenance Activities - Emission Factors for Solvent Degreasing

Solvent degreasing within the zinc processing industry is related to maintenance activities.
Table 6.3 contains emission factors for solvent emissions.

Table 6.3 - Emission Factors for Solvent Emissions

Solvent Used Use Emission Factor1 Emission Factor
(kg/kg solvent used) Rating
Dichloromethane
Vapour
Uncontrolled Degreasing 0.930 E
Controlled Cold Cleaners 0.890 E
Tetrachloroethylene
Vapour
Uncontrolled Degreasing 0.890 E
Controlled Cold Cleaners 0.850 E
Trichloroethylene
Vapour
Uncontrolled Degreasing 0.910 E
Controlled Cold Cleaners 0.870 E
1
Emission Estimation Technique Manual for Ferrous Foundries (National Pollutant Inventory, 1998

Zinc Concentrating, Smelting and Refining 49

7.0 Emissions to Water

7.1 Background

Emissions of substances to water can be categorised as discharges to:

• Surface waters (eg. lakes, rivers, dams and estuaries);

• Coastal or marine waters; and
• Stormwater.

Groundwater is not considered as a “water body” within the context of NPI reporting.
Groundwater is included as an emission to land.

Significant emissions to water within the zinc concentrating, smelting and refining
industry, including the ancillary activities and associated facilities, will be related to:

• Run-off and erosion from the concentrating and processing areas (refer to the EET
Manual for Mining);
• The discharge of treated process waters (such as treated TSF decant water and from an
effluent treatment plant);
• The discharge of sewage and domestic wastewaters; and
• Spills to surface waters.

The most accurate techniques for estimating emissions to the environment via wastewater
is likely to be direct measurement. However, facilities may use other EETs for the
purposes of reporting within the NPI.

7.1.1 Run-off and Erosion

Run-off and sediment eroded from a site may contain metals. The efficiency of the
existing stormwater management program will determine the amount of sediment in run-
off. Actual emissions will be highly dependent on the weather conditions over the
reporting period and a function of the size of the catchment. At some facilities, run-off is
collected, treated and reused in the processing plant, thus it is now classified as a transfer
rather than an emission.

Direct Measurement

Site-specific information on water quality and flow rates can be used to characterise
emissions. Water quality is likely to be routinely monitored and flow rates from specific
catchments may be known from monitoring or from estimations based on calibrated
models or engineering calculations eg. Australian Rainfall and Run-off.

Zinc Concentrating, Smelting and Refining 50

Mass Balance

Emissions of metals to water may be estimated through the use of a mass balance. This
technique requires the quantification of total materials into and out of the process with the
difference being accounted for in terms of releases to air, water and land or as transfers.

7.1.2 Discharge of Treated Process Waters

The majority of smelters and refineries have effluent treatment plants (ETP) to treat
process water and sometimes, when necessary, stormwater run-off. These plants are
based on the manipulation of pH levels by the addition of chemicals such as sodium
hydroxide to enable the precipitation of heavy metals in the solution in the form of metal
hydroxides. The precipitated metals are then recycled to the smelting or leaching process
or can be sold. The resulting effluent is then discharged off-site, generally in accordance
with licence requirements.

Direct Measurement

If monitoring of metal levels and the flow rate is required as part of the licence conditions
for discharge, then the metals emitted from the site are known.

Mass Balance

This technique can be used in conjunction with direct monitoring to estimate emissions to
water.

7.1.3 Discharge of Sewage and Domestic Wastewaters

Direct Measurement

Total nitrogen and total phosphorus loadings may be estimated by direct measurement
based on:

• Wastewater flows; and

• Representative concentrations of total nitrogen and phosphorus in wastewater flows.

Direct measurement is applied to “end of pipe” emissions ensuring that the facility-
specific efficiency of wastewater treatment plants is fully considered.

Zinc Concentrating, Smelting and Refining 51

Emission Estimation

The example presented below is based on generic emission factors and provides indicative
facility population levels likely to result in exceedence of Category 3 thresholds.

Based on the West Australian Water Corporation wastewater treatment design criteria, the
per person per day loading of total nitrogen and phosphorus has been calculated
(Table 7.1). This data has been applied to the NPI reporting thresholds to provide an
indicative facility population that will result in exceedence of the reporting thresholds.

Table 7.1 - West Australian Water Corporation Wastewater Treatment Design Criteria
for Total Nitrogen and Phosphorus
kg per person per day Indicative Facility Population

Total nitrogen 0.011 >3500

Total phosphorus 0.0025 >3000

Assumes: - Annual dry weather flow of 200 litres(L) per person per day;
- Total nitrogen concentration of 55 mg/L (range of 40-70);
- Total phosphorus concentration of 12.5 mg/L (range of 10-15); and
- 365 days per year of nitrogen and phosphorous loading.

Estimation of total nitrogen and total phosphorus emissions may be made using the
equation shown below:

Equation 7.1
1− E
MNorP = MNorP * Npers * Ndays *
100

where:

MNorP = mass of total Nitrogen or Phosphorus emitted (kg)

MNorP = average loading of Nitrogen or Phosphorus per person per day (kg/p/d)
Npers = average number of personnel on-site
Ndays = number of days of loading to the sewage treatment system
E = efficiency of sewage treatment system

7.1.4 Spills to Surface Water

If spills occur, it is unlikely that the amount discharged is accurately known. In this case
an estimate of the volume may be able to be made and previous data on direct
measurement can then be used to derive the accidental emission.

Zinc Concentrating, Smelting and Refining 52

8.0 Emissions to Land
8.1 Background

Emissions of substances to land on-site may result from solid wastes, slurries, sediments,
spills and leaks, storage and distribution of liquids, and the use of chemicals to control
various elements of the environment where these emissions contain listed substances
(such as fertilisers and pesticides). These emission sources can be broadly categorised as:

• Surface impoundments of liquids and slurries, such as TSFs;

• Storage of, or transfer to waste storage facility, of slag or jarosite; and
• Unintentional leaks and spills.

In relation to the zinc concentrating, smelting and refining industry, discharges to land
such as TSFs, solid waste dumps and waste rock dumps are classed as transfers.
Emissions from these transfer facilities to the environment are, however, included within
the scope of the NPI and will generally be addressed as either emissions to groundwater
(land) or to air.

8.2 Groundwater Modelling - Fates and Trajectories

Groundwater movement may be modelled to allow prediction of groundwater fates and

that of any associated dissolved substances. Additionally, modelling will allow the
temporal prediction of groundwater movement allowing the potential for the breakdown
of substances within the groundwater or their in-situ adsorption to be estimated.

Groundwater models may be based on limited data such as calculated groundwater flow
rates and direction, or contain in-depth data such as the geology and hydrogeology of the
area. The complexity of models should be stated when used to estimate emissions in
order to ensure that the error bands associated with the reported data are fully
appreciated.

The fate of dissolved metals resulting from TSF seepage would be suited to this approach.

8.3 TSF Seepage

8.3.1 Direct Measurement

Seepage from TSFs may be estimated through the use of a system of monitoring bore
holes.

Borehole layout and depths will be dependent on facility-specific conditions, such as

hydrogeology, depth to groundwater and groundwater flow direction. However, in order
to achieve an accurate estimation of emissions, such as cyanide and metals, boreholes
should:

• Intercept known preferential flow paths; and

• Be located at a range of distances from the TSFs.

Zinc Concentrating, Smelting and Refining 53

 A: Bores within
retaining walls

TAILINGS
B: Monitoring and
STORAGE
/or recovery bores
FACILITY

C: Monitoring
bores

Figure 8.1 - Bore Hole Arrangement for TSFs

Figure 8.1 displays a typical arrangement for bore hole placement, it should be noted that
alternative recovery systems (such as trenches) may also be used. NPI substances detected
(above background levels) at bores “B” (monitoring and/or recovery) will not be
considered as emissions to the environment if recovered water is treated, for example
pumping back to the TSF. The substances contained in the volume of water not recovered
will be considered as emissions to the environment.

NPI substances detected (above background levels) at bores “C” (monitoring) will be
considered as emissions to the environment.

The mass of NPI substances emitted will be estimated by multiplying the detected
concentration at bores “B” by the known hydraulic loading beyond bores “B” (from the
zone of influence and hydraulic conductivity of the soil) and the monitoring interval.

The hydraulic loading around the TSF is estimated using the equation below. The
equation may be used to estimate the hydraulic loading from all “faces” of the TSF (north,
south, east, and west) as a single entity or in distinct areas where the hydraulic gradient is
known to differ significantly.

The hydraulic gradient is based on the hydraulic head produced by the TSF and the
physical gradient between bores “A” and “B”.

Equation 8.1
YTSF = Ainfl * Khyd * Ψhyd

where:

YTSF = TSF hydraulic loading (m3/day)

Ainf = cross sectional area of zone of influence (m2)
Khyd = hydraulic conductivity (m/day)
Ψhyd = hydraulic gradient

The Emitted Hydraulic Loading is estimated by subtracting the volume of recovered water
from the TSF Hydraulic Loading.

Zinc Concentrating, Smelting and Refining 54

Equation 8.2
Yemit = YTSF - VH20

where:

Yemit = emitted hydraulic loading (m3/day)

YTSF = TSF hydraulic loading (m3/day)
VH20 = volume of recovered water (m3/day)

The emission of NPI substances is then estimated.

Equation 8.3
M = CB * Yemit * T

where:

M = mass of substance emitted (kg)

CB = concentration of substance in bores ‘B’ (kg/m3)
Yemit = emitted hydraulic loading (m3/day)
T = period (days)

8.3.2 Modelling

Seepage from TSFs is generally accounted for as part of the design criteria and should not
be viewed as a failure of the containment system.

Modelling of seepage from TSFs is recognised as an appropriate means of designing and

operating TSFs. Models may be used to estimate emissions of dissolved substances such
as cyanide and metals.

There are many commercial models available. Models include PC-SEEP, a two
dimensional unsaturated/saturated groundwater flow model (Mt Keith Nickel, 1996).

8.3.3 Mass Balance

Water Balance

Tailings Storage Facilities (TSFs) represent a significant potential emission source of some
NPI substances. A comprehensive water balance, refer to Figure 8.2, will assist in the
identification and quantification of emission pathways, allowing the emission pathways of
soluble and volatile substances to be more accurately identified and estimated (Source:
BPEMIM, Cyanide Management, 1995).

Zinc Concentrating, Smelting and Refining 55

 Process waters TSF return

Rainfall Evaporation
TSFs

Recovered Retained
bore water water
Borehole
monitoring

Seepage

Emissions to
groundwater

Figure 8.2 - TSF Water Balance

A comprehensive water balance, when used in conjunction with EETs, will facilitate the
estimation of emissions of soluble NPI substances (such as metals) from TSFs.

For example, the difference between known water inputs and losses (including rainfall
and evaporation) in the water balance can normally be assumed to represent seepage.
Emissions of soluble NPI substances may be estimated through direct measurement of
monitored boreholes and relating this data to the known hydraulic conductivity of the
soils.

It is noted, however, that estimates of the inputs/outputs of some water balances may
have significant associated error bands. Work recently undertaken by MERIWA
demonstrates the errors that may be associated with the calculation of evaporative losses
from the surface of TSFs. This is well illustrated by the following example from MERIWA
Project Report M241m 1998;

For a TSF of 100 ha, an evaporative loss of 100 mm is equivalent to a

3
total volume of 100 000 m .

Evaporative losses are influenced by a wide variety of factors.

Increasing salinity may reduce evaporation by as much as 60-95% of
the potential evaporative rate. As such estimating to an accuracy of
100 mm may require extensive study and characterisation and any
errors in calculating these losses may result in significant
inaccuracies.

Zinc Concentrating, Smelting and Refining 56

Metals in Water

Metals may be emitted:

• Through seepage from TSFs and heap/dump leach pads;

• As dust; and
• As a result of TSF overflow.

The mass balance approach may be utilised to estimate emissions of metals in a manner
similar to that used to estimate the emission of cyanide through seepage.

While these seepage rates will be facility-specific, generic seepage rates of between 0 – 10%
of return waters have been quoted within the nickel industry (Mt Keith Nickel 1996,
ANCOLD, pers. Comm.) and can be applied to the zinc industry.

The mass of reportable NPI metals lost to the environment through seepage may be
estimated using:

• Estimates of seepage rate; and

• The concentration of NPI metals in TSFs return water or dump/heap leach liquors.

The retention of NPI metals by the TSF, or pad liner, or under liner. If this is not known,
assume retention is zero.

Metal concentrations should be assumed as being equal to that in the TSFs return water
unless facility-specific data suggests otherwise.

Equation 8.4
MM = CM * Vslurry * V/100

where:

MM = mass of metal emitted through seepage (kg)

CM = concentration of metal (kg/m3)
Vslurry = volume of water/slurry throughput to TSF per year (m3)
V = seepage rate (%)

Where data on the permeability of TSF construction material is known Darcy’s Law may
be applied to calculate hydraulic loadings to the environment. Darcy’s Law is most
applicable where an impermeable membrane has not been installed as part of the TSF
design. Where an impermeable membrane has been installed but seepage is known to be
occurring, Darcy’s Law may be applied to facilities that estimate the surface area of the
liner where its integrity has been compromised.

Zinc Concentrating, Smelting and Refining 57

Equation 8.5
  dh  
Vseepage =  K * A * S y *  dl  
  
where:

Vseepage = volume of calculated seepage (m3/day)

K = vertical permeability of TSF floor material (m/day)
A = surface area of TSF cell floor (m2)
Sy = specific yield of tailings materials (%)
dh = thickness of tailings in the cell (m)
dl = hydraulic head above floor of the cell (m)

Specific yield (Sy) is the amount of water potentially released by the tailings material. For
example, where the saturated moisture content of the tailings is known to be 10%, the
specific yield may be half of the saturated moisture content and would be expressed as 5%.

The seepage would be applied to the equation below to estimate emissions:

Equation 8.6
EM = Vseepage * Ndays * CM

where:

EM = emission of the metal (kg)

Vseepage = as above (m3/day)
Ndays = number of days TSF operated (days)
CM = concentration of metal (kg/m3)

In the absence of facility-specific data, the following data should be used in calculating
seepage:

• 10% seepage rate of return waters;

• Metals concentration equal to that in TSFs return water; and
• No bore water recovery.

Metals may be retained in the TSF or pad liner or under-liner. If test data on metals
retention is available, a more accurate estimate may be obtained. If no data are available,
assume retention is zero.

Borehole recovery may be factored into the estimation technique where metal
concentrations and volumes of recovered bore water are known.

Equation 8.7
MM-seepage = MM-bore - CM-bore * Vbore-water
where:

MM-sepage = mass of metal emitted through seepage (kg)

MM-bore = mass of metal emitted through recovered bore water (kg)
CM-bore = concentration of metal in bore water (kg/m3)
Vbore-water = volume of recovered bore water (m3)

Zinc Concentrating, Smelting and Refining 58

9.0 Examples of Application of EETs

9.1 Sulfur Dioxide

9.1.1 Background

As there are considerable quantities of sulfur in the zinc sulfide ores (Section 2.1),
significant sulfur dioxide (SO2) emissions occur at various processes associated with
primary zinc smelting. Recovery of this SO2 for the production of sulfuric acid is good
environmental practice and may be economically beneficial. Typically the gas is captured
and piped to an acid plant for the manufacture of sulfuric acid.

The use of a sulfuric acid plant to treat zinc smelter effluent gas streams requires that
particulate-free gas streams with a steady SO2 concentration of at least three percent are
maintained.

The remaining smelter operations process material containing very little sulfur, resulting
in insignificant SO2 emissions. Particulates may be emitted from fire-refining operations.
Electrolytic refining emissions are negligible.

Sulfur dioxide not released through a vent or stack is classified as a fugitive emission.

The EET Manual for Nickel Concentrating, Smelting & Refining (Nickel EET Manual) provides
detailed examples of how the emission estimation techniques can be applied to various
emissions, and the discussion below is based on this. The following techniques can be
used to estimate the amount of SO2 emitted.

9.1.2 Direct Measurement

Direct measurement (or source monitoring) is one of the most accurate methods of
estimating emissions of SO2. Usually, SO2 emissions are measured at the stack exit points.
The gas is emitted from the sinter machine and the main furnace, as well as from the
roasting furnace. All these areas also contribute to fugitive emissions.

Most smelters have stack-monitoring programs designed to meet environmental licence

conditions. These conditions generally specify an amount of SO2 that is not to be exceeded.
Ambient SO2 is also measured to meet environmental and health-related goals.

Elements of the processing of zinc are also regularly monitored in order to optimise the
recovery of the product eg. the efficiency of the gas collection and treatment system to
ensure that the maximum amount of gas is directed to the acid plant to make sulfuric acid.

Direct measurement data can be used to calculate actual amounts emitted to the
environment, by multiplying the concentration of SO2 in the final emission stream (stack
emission) by the mass of the emission stream:

Zinc Concentrating, Smelting and Refining 59

Equation 9.1
 273 
MSO2 = CSO2 * VSO2 *  
 273 + T 
where:
E SO 2 = emission of sulfur dioxide (kg/hr)
CSO 2 = concentration of SO2 (kg/m3)
VSO 2 = stack gas volumetric flow rate (m3/hr)
T = temperature (oC)

Direct measurement is generally undertaken according to standard sampling and

monitoring procedures in compliance with the environmental conditions specified in the
licence. If direct measurement is to be undertaken outside this regulatory system, then
sampling and monitoring should be undertaken in accordance with Australian standards.

9.1.3 Mass Balance

This technique provides an estimate of emissions where known quantities of a substance

are supplied to a process and the process fate of the substance is both known and
quantifiable.

It is imperative that the mass balance calculations address all losses and fates of a
substance and utilises best available data. This approach allows fugitive and other
emissions to the environment to be estimated.

Sulfur dioxide emissions from converter and smelter operations may be estimated through
the use of a mass balance. However, the greater the level of accuracy applied to the
process inputs and outputs, the more accurate the estimate of emission will be. Figure 9.1
shows a simplified approach to SO2 emissions from sinter/smelter operations.

Air Emissions
(fugitives, stacks)

Sinter/
Feedstock & Fuel Product
Smelter

Solid Waste
Figure 9.1 - Estimating SO2 Emissions

The weight percent of sulfur (as elemental S) in the fuel and feedstock (concentrate and
flux) is used to estimate the total inputs to the process. Outputs are based on
representative sampling of the product (matte or anode zinc) and waste (slag or slimes).

Zinc Concentrating, Smelting and Refining 60

Example 9.1 - Mass Balance Technique for Estimating SO2

In the example presented (refer to Figure 9.2), stack emissions are estimated through
representative sampling, allowing the fugitive emissions to be estimated. However, direct
measurement of stack emissions is not required to effectively estimate emissions using a
mass balance approach.

In this example, SO2 emissions are calculated based on the sulfur content of the input and
output streams. The quantity of SO2 that may be produced from each stream is calculated
by multiplying the concentration of sulfur by 2 (= MWSO2/EWS = 64/32). For example, the
flux stream contains 715 tonnes of sulfur, which will produce 1430 tonnes of SO2.

Where data is not available estimates may be used and any shortfalls assumed to be losses
to the environment. While there are many variables in the mass balance, the errors
inherent in this approach may be minimised through continued development and
refinement of the mass balance equation.

Flux
(A2) - 1430 tonnes

Concentrate
(A1) - 165 950 tonnes
Fuel
(A3) - 190 tonnes

Fugitives Flash furnace slag

Sinter/ (B) - 3520 tonnes

Smelter Other waste gases

(C) - 27 150 tonnes
Acid Plant

Final Matte Product

H2 SO4 product Acid Plant (F) - 25 860 tonnes
(E) - 110 000 tonnes Gases
(D) - 130 tonnes

Figure 9.2 - Mass Balance SO2 Calculations for Example 9.1

Inputs = Estimated Outputs + Assumed Outputs

A1+A2+A3 = (B + E + F) + (D + C) + Fugitives
167 570 = (139 380) + (27 280) + Fugitives
Fugitives = 167 570 - 166 660
Fugitives = 910 tonnes

Zinc Concentrating, Smelting and Refining 61

9.1.4 Emission Factors

It is unlikely that any zinc processing facilities in Australia would need to use emission
factors for estimating sulfur dioxide emissions, because most sites are required to monitor
sulfur dioxide under licence conditions and can use direct measurement or at least a mass
balance.

The US EPA publishes emission factors for various industries in the document known as
AP-42, which is periodically updated and is available on the internet. The AP-42 chapter
on zinc smelting contained no emission factors for sulfur dioxide as of May 1999.
Chapter 12.7 Zinc Smelting includes the following discussion:

The roasting process in a zinc smelter is typically responsible for more than 90
percent of the potential sulfur dioxide emissions. About 93 to 97 percent of the
sulfur in the feed is emitted as sulfur dioxide. Typical sulfur dioxide concentrations
for multiple hearth, suspension, and fluidised bed roasters are 4.5 to 6.5 percent, 10
to 13 percent, and 7 to 12 percent, respectively. Various combinations of control
devices such as cyclones, electrostatic precipitators (ESP), and baghouses can be used
on roasters and on sintering machines, achieving 94 to 99 percent emission
reduction.

9.2 Cyanide

9.2.1 Mass Balance

Sodium cyanide may be used in zinc concentrating as an iron depressant. It is likely that
most zinc concentrating, smelting and refining facilities will trigger the reporting
threshold for cyanide.

The NPI requires that inorganic cyanide compounds are reported where the threshold is
triggered. As such when estimating emissions of cyanide to the environment, it is
important that total cyanide is reported where the CN mass is not known.

Cyanide fates within the process and TSFs are extremely complex. Evaporation,
reduction, oxidation, precipitation, adsorption, desorption, and exchange reactions are just
a few of many possible simultaneous events. All cyanide is ultimately decomposed or
forms complexes within the TSFs. Cyanide can be emitted to air, water, and land. This
example includes all three emission media as the mass balance approach accounts for all
input and output sources.

A mass balance approach may be employed to develop a flow diagram of cyanide

additions and losses to the process. It is likely, however, that other EETs, such as direct
measurement and modelling will support the mass balance approach, in order to increase
the accuracy of estimated emissions.

Zinc Concentrating, Smelting and Refining 62

Cyanide Emissions from Storage and Mixing Areas

Cyanide emissions from storage and mixing areas will mainly be due to spillage losses
and may be estimated through effective record keeping of all spills and inventories of
supplies. These emissions will be classed as emissions to land.

Losses to ground and water may be differentiated through effective record keeping of all
spills, and the fate of spilled material (washed to treatment process, absorbed and
disposed of to licensed site etc.).

Cyanide Emissions from the Ore Processing Area

A mass balance approach (based on Figure 9.3) may be used to estimate the emissions of
cyanide through the volatilisation (and other losses such as carry over with product).

Equation 9.2
MVCN = MCN + MCNreturn - MCNTSF - MCNneut - MCNseep

where:

MVCN = mass of cyanide lost through volatilisation (kg)

MCN = mass of cyanide added to the process (kg)
MCNreturn = mass of cyanide in TSF return water (kg)
MCNTSF = mass of cyanide carried to TSF (kg)
MCNneut = mass of cyanide neutralised prior to TSF (kg)
MCNseep = mass of cyanide loss in seepage from TSF (kg)

Cyanide (NaCN) Cyanide (HCN)

addition to Zinc volatilisation
system Process

Cyanide carry through Seepage

with process water / slurry

TSF water return

Figure 9.3 - Cyanide Emissions

Zinc Concentrating, Smelting and Refining 63

Cyanide Emissions from TSFs

Figure 9.4 illustrates the mass balance approach to cyanide emissions from TSFs.

Carry through with

process water /slurry TSFs water return

HCN
volatilisation
Recovered TSF
bore water Cyanide Discharge of
decomposition treated waters

Emissions to ground/
Seepage groundwater

Figure 9.4 - Mass Balance Approach to Cyanide Emissions from TSFs

Cyanide may be emitted to the environment via the following pathways:

• Seepage; and
• Volatilisation

Seepage

The mass of cyanide lost to the environment through groundwater seepage may be
estimated using:

• Seepage rates; and

• The concentration of total cyanide in TSFs return water in monitoring bores.

While these seepage rates will be facility-specific, generic seepage rates of between 0 - 10%
have been quoted within the industry (Mt Keith Nickel 1996, ANCOLD pers. Comm.
Referenced in the Nickel EET Manual). The 10% figure can be used as a point of reference
for reporting purposes. Alternatively the seepage load calculated using Darcy’s Law can
be applied (refer to Section 8.3).

Cyanide concentrations in seepage may be assumed as being equal to that in the TSFs
return water (total cyanide) unless facility-specific data suggests otherwise.

Zinc Concentrating, Smelting and Refining 64

Equation 9.3
MCNS = Vslurry * V/100 * CCN

where:
MCNS = mass of cyanide emitted through seepage (kg)
Vslurry = volume of water/slurry throughput to TSF per year (m3)
V = seepage rate (%)
CCN = concentration of cyanide (kg/m3)

In the absence of facility-specific data the following parameters may be used in calculating
seepage:

• 10% seepage rate;

• Total cyanide concentrations equal to that in TSFs return water in monitoring bores;
and
• No bore water recovery.

Borehole recovery may be factored into the estimation technique where cyanide
concentration, and volumes of recovered bore water are known.

Volatilisation

In natural degradation most “free” cyanide is lost through volatilisation (BPEMIM,

Cyanide Management, 1998). The cyanide is volatilised as HCN, which ultimately breaks
down to form ammonia and carbon dioxide.

At present there is no reliable method for estimating emissions of cyanide from TSFs using
a mass balance. The emission factors for volatilisation from TSFs presented below may be
used to estimate these emissions.

9.2.2 Emission Factors

Cyanide Emissions from the Ore Processing Area

Based on research carried out by CSIRO it is estimated that 1% of total cyanide is lost
through volatilisation as HCN within the processing area of gold operations
(Heath et al, 1998). This estimate is assumed to be applicable to the zinc processing
industry for the purposes of this manual.

Zinc Concentrating, Smelting and Refining 65

Emissions should be reported as mass of CN– using the stoichiometry detailed below:

Equation 9.4
M CN − = MHCN * 0.54

where:
M CN − = mass of CN- emitted (kg)
MHCN = mass of HCN (as kg of NaCN emitted)
0.54 = the stoichiometry

Cyanide Emissions from TSFs

It has been estimated that volatilisation of HCN accounts for 90% of the natural
degradation of cyanide from TSFs within the gold industry (Ellis, 1997; Simovic, 1984) and
is assumed to be the case for the zinc processing industry for the requirements of this
manual.

Volatilisation is, however, extremely pH dependent as a result of the HCN/CN- flux. A

range of other factors also influences the rate of volatilisation although pH is the most
significant factor.

This percentage degradation is dependent, however, on pH conditions. Where “free”

cyanide concentration and pH of the TSF return water are known the percentage
degradation may be estimated based on the conditions detailed in Table 9.1.

Table 9.1 - Percentage of Natural Degradation of Cyanide Due to Volatilisation

Percentage of Natural Degradation Due to
pH
Volatilisation
6 90%
7 90%
8 80%
9 60%
10 20%
11 0%
12 0%
(Source: Based on Ellis, 1997; Simovic, 1984)

This data is applied using the equation below:

Zinc Concentrating, Smelting and Refining 66

Equation 9.5
MVHCN = CCN− * Vslurry * V/100

where:

MVHCN = mass of HCN volatilised from TSFs (kg)

CCN− = free cyanide concentration in TSF return water (kg/m3)
Vslurry = volume of water/slurry throughput to TSF per year (m3)
V = volatilisation rate (%)

9.3 Carbon Disulfide

The Nickel EET Manual discusses the use of emission factors for carbon disulfide. This
section of the Nickel EET Manual has been adapted for this manual and follows.

Sodium ethyl xanthate (SEX), C2H5OS2Na, is widely used in Australia in

flotation/concentration processes. SEX is used as a collector, to alter the
hydrophobic/hydrophilic nature of the mineral surface, which aids in the flotation of the
sulfide complexes. It decomposes in the presence of moisture and/or heat to produce
carbon disulfide, which is an NPI reportable substance. When SEX is used as a flotation
agent it is mixed with water, usually at a concentration of approximately 10%. The
majority of the SEX is retained within the froth that contains the zinc concentrate, whilst
the remainder (approximately 1%) will report to the TSF. The ultimate fate and
decomposition of xanthate is not fully known. However for the purposes of NPI reporting
it can be assumed that 0.2% of SEX will decompose hydrolytically to release carbon
disulfide (CS2).

Xanthate breakdown is influenced by a number of factors. Within the zinc concentrating,

smelting and refining industry the most significant of these factors are:

• pH (below pH 7 the xanthate decomposition rate increases dramatically); and

• Temperature (10°C rise in temperature may cause a threefold increase in
decomposition rates).
[Source: WMC Report Ref 692 634, 1992]

The stoichiometry of xanthate decomposition, and hence CS2 formation, will also vary
according to the pH.

• Hydrolytic decomposition (alkali conditions) of the xanthate ion results in a

stoichiometry of 1:0.5 (xanthate to CS2); and.
• Hydrolysis decomposition (acidic conditions) of the xanthate ion results in a
stoichiometry of 1:1 (xanthate to CS2).
[Source: WMC Report Ref 692 634, 1992]

Zinc Concentrating, Smelting and Refining 67

The decomposition stoichiometry will vary with the form of xanthate used at particular
facilities. Facilities should verify the stoichiometry to be applied based on their use of
xanthate types.

Depending on the process operation at a particular site the zinc concentrating, smelting
and refining area will generally be alkaline. However at some facilities this may be very
difficult to achieve. TSFs are also likely to be alkali, although the geochemistry of the ore
being handled may result in the TSF becoming acidic.

As the first point of reference, it can be assumed that 100% degradation of xanthate occurs
within the processing area, with 0.2% of the degraded xanthate converting to carbon
disulfide.

On this assumption CS2 emission may be estimated using the equations:

Equation 9.6a
Alkali Conditions (pH>7):

MWCS 2
Moles of CS2 emitted (kg) = 0.2% * 0.5 * Mass of Xanthate *
MWxanthate

Equation 9.6b
Acidic Conditions (pH<7):

MWCS 2
Moles of CS2 emitted (kg) = 0.2% * 1.0 * Mass of Xanthate *
MWxanthate

Example 9.2 - Breakdown of Xanthates

A facility uses 150 kg of Sodium Ethyl Xanthate (SEX) and for each mole of SEX used,
0.5 moles of CS2 are produced (alkali conditions)

Molecular weight of CS2 ( MWCS 2 ) = 76g

Molecular weight of SEX ( MWSEX ) = 144g

MWCS 2
Emissions of CS2 (kg) = 0.002 * 0.5 * Mass of Xanthate *
MWxanthate
= 0.002 * 0.5 * 150 kg * 76 g/144 g
= 0.08 kg

Zinc Concentrating, Smelting and Refining 68

10.0 Best Practice

The NPI Guide has been developed to provide information on the type and extent of
emissions from Australian industries. Encompassed in the reporting requirement is
addressing how emissions will be reduced. Best practice requires every reasonable effort
on behalf of the company to minimise emissions. The results of these efforts are evident in
the introduction of new processing methods such as the ISASMELT smelting process,
developed by Mt Isa in conjunction with the CSIRO, which has reduced the quantity of
airborne pollutants.

When reducing the emissions from a zinc processing facility there are three recommended
approaches:

1. Process modification: This not only includes using different equipment and reagents
that produce less reportable emissions but also encompasses the integration of process
streams to maximise energy transfer and the utilisation of by-products, eg. the
formation of sulfuric acid. In addition, the NPI trigger levels for Category 1 and 1a
substances are not based on the concentration leaving the facility but on the amount
“used”, thus process modification also includes changes in inventory handling and
control.
2. Containment: Where possible all ore, feed products, waste, reaction equipment and
product should be contained, either in sealed containers, bunded, in dams, or within a
room under negative pressure. If not contained suitable mechanisms should be
incorporated to reduce the likelihood of emission, e.g. using a windbreak around
stockpiles, tarps on trucks.
3. Treatment: All discharge streams should be treated prior to release: this includes
removal of all dust from gases before they are vented and the processing of effluent
through a trade waste facility

Appendix B of the NPI Guide lists additional emission reduction activities, including
inventory control, spill and leak prevention, raw material modifications, process
modifications, cleaning and degreasing, surface preparation and finishing, and product
modifications. This appendix also includes the Activity Codes that should be quoted
when reporting reduction activities.

Emission control technologies commonly used in the Australian lead processing industry
are considered in the following sections. These technologies, in some companies, are
combined with environmental management systems to reduce the overall adverse
environmental impact of zinc processing.

10.1 Control Technologies for Air Emissions

Air emissions are measured at the point of creation, this does not take into account the fate
of the emission, eg. sulfur dioxide is measured at the stack, not the site boundary. The
three main components of air emission produced at a zinc smelter/refinery are dust, metal
fumes and sulfur dioxide gas.

Zinc Concentrating, Smelting and Refining 69

10.1.1 Concentrating

A site can minimise air emissions from ore concentrating if they:

• Enclose part or all the process area;

• Keep ore damp, where possible;
• Utilise wet spray suppression systems;
• Enclose transfer points, equipment and the truck loading operation;
• Wet and cover truck loads and stored concentrates;
• Use sprinkler systems on unloading area and stockpiles;
• Incorporate preventative maintenance on machinery to minimise leaks; and
• Store all chemical feeds to the flotation cell in sealed containers.

Tailings Dams

There are two potential air emissions from tailing dams - cyanide and dust. To minimise
these emissions facilities may:

• Utilise a wind break to minimise dust generated by the wind;

• Revegetate the dam; and
• Monitor the level of cyanide vaporising.

10.1.2 Processing Site

For loading and unloading areas the following measures should be considered:

• Enclose the areas, where possible;

• Where it is not practical to enclose the area, water spray suppression systems should be
installed on the unloading and loading facilities; and
• Reduce the amount of raw materials stored outside.

For the storage of raw materials:

• Minimise the amount of raw materials stored outside, maximise storage in sealed bins;
• Sealing compounds should be used for outside storage; and
• Where sealed compounds are not used, it is recommended that the area be protected to
minimise exposure to wind eg. a wetting system or wind barrier.

Sinter Plant

• Enclose the vibratory feeders and screens, where possible, and duct gases to a scrubber
or fabric filter;
• Collect the hot gas from the front of the sinter plant and directed to an acid plant or a
scrubber;
• Pass the gas from the rear of the sinter plant through a scrubber before being emitting
into the atmosphere or recirculate the gas back through the sinter after it passes
through a cyclone;

Zinc Concentrating, Smelting and Refining 70

• Operate the sinter building (fugitive emissions) under negative pressure;
• Enclose conveyors, screw, shakers etc., and ensure preventative maintenance is
undertaken;
• Collect post sinter activities (breaker, rolls, screens) emissions and pass through a
venturi scrubber and stack;
• Recycle sinter fines back into the sinter plant; and
• Equip sinter bins with bin vent filters.

Smelting/Refining

• Furnace gases should be directed to a fabric filter;

• Fugitive emissions in the smelter building include dust from uncovered screws and
conveyors, discharges from charge outlets, leaks from furnace covers etc. Controls
include the enclosure of conveyors and other material handling equipment, where
practical, operating the building under negative pressure and having a preventative
maintenance program in operation; and
• Collect dust and fumes and direct to a fabric filter.

Fuel Storage

There are three main options available to handle emissions from fixed roof tanks. As
emissions are directly related to vessel capacity, organic properties of the liquid, tank
turnover rate and atmospheric conditions, modification of existing structures provide the
best control mechanisms. Options available are:

• Installation of an internal floating roof can dramatically reduce evaporation emissions

from fixed rook tanks by 60-90 percent;
• Vapour balancing, essentially vapours are trapped in an empty vessel while the storage
vessel is being filled. This vessel is then transported to a vapour recovery system or
vented to the atmosphere (the latter providing essentially no control). Vapour
recovery can produce control efficiencies ranging from 90 to 98 percent; and
• Vapour recovery systems: these systems condense the collected vapours for reuse.
Common units utilise vapour compression, vapour cooling, vapour/solid adsorption
and vapour/liquid absorption.

10.1.3 Site

Other dust control measures include:

• Internal roads that are not sealed should be dampened regularly, or alternatively
treated with dust suppression chemicals or oils (subject to EPA approval);
• Sealed internal roads should be regularly cleaned and washed, with contaminated
water being collected, treated and recycled;
• Landscaping and sealing of stockpiles; and
• Utilisation of fabric filters, scrubbers and stacks to treat point source emissions.

Zinc Concentrating, Smelting and Refining 71

10.2 Control Technologies for Water Emissions

Water emissions include discharges from boiler blow-down, process water from the
various activities and floor and site drainage including contaminated stormwater. Zinc
processing facilities utilise large quantities of water each year, and this process water
cannot go straight to sewer so it must either be treated or reused within the facility.

A range of wastewater treatment techniques is used to reduce the adverse environmental

impact of water discharges. Examples of such techniques include:

• All drainage points should feed to an impoundment facility, so no liquid waste flows
direct to sewer;
• Use of storm water containment facilities;
• Control of floor drain discharges via oil and silt interceptors;
• Recycling of process water wherever practicable;
• Prompt repair of all leaks;
• Use of reed-bed filtering lagoons to minimise water disruption in dams during
seasonal storms; and
• Recovery of treated effluent and contained stormwater, for use for dust suppression.

10.3 Control Technologies for Land Emissions

Land discharges are limited to waste materials, ash (for coal fired plant) and ground water
contamination.

Control techniques include:

• Utilisation of flyash for cement products;

• Passing gases through a filter system to reduce particulate emissions;
• Controlled waste landfill or disposal off-site;
• Wet ash dams (not impacted by wind erosion);
• All vehicles and machinery transporting concentrate, should be washed down due to
the potential for cross contamination;
• Closely monitoring seepage from containment facilities into ground water;
• Lining of tailings dams to minimise ground-water contamination;
• Inspection and monitoring program of potential spill or leak sources; and
• Bunding of oil, fuel, electrolytic cells and chemical storage, to reduce the risk of
spillage to soil.

Zinc Concentrating, Smelting and Refining 72

11.0 Glossary of Technical Terms and Abbreviations

11.1 Definitions

Reference should be made to the National Pollution Inventory and the NPI Guide for
definition of terms used within the NPI system.

Boundary Boundary is defined in various ways depending on the

emission type. For emissions to air boundary is the point of
creation (such as the surface of a liquid for evaporation, or the
wheels of a vehicle for dust generation). For emissions to land
and water, boundary is the point at which a substance is no
longer contained (such as a spill to ground from a process
vessel, or a discharge to surface waters from a treatment
works).
Direct Measurement Technique used to estimate emissions to the environment
through the sampling and analysis of emission streams.
Emission Any release of substances to the environment whether it is in a
pure form or contained in other matter. Emissions may be
solid, liquid or gaseous.
Emission Factor A number or equation that may be applied to raw data from a
facility to estimate emissions from that facility without the
need for emissions sampling and analysis. This technique is
most often used to estimate gaseous emissions to the
environment.
Fugitive Emissions Emissions not released from a vent or stack.
Inventory Means of recording usage and stores of all materials, and
product, held on a facility or utilised by a process.
Mass Balance Technique Estimation of emissions to the environment through
equalisation of inputs and outputs to a particular process or
facility.
Power Generation Production of power for the operation of facilities and use in
processes.

Zinc Concentrating, Smelting and Refining 73

11.2 Abbreviations

API American Petroleum Institute

C Capacity
CO Carbon monoxide
DCAP Double Contact Acid Plant
DoME Department of Minerals and Energy
DM Direct Measurement
EC Engineering Calculation
EEA European Environment Agency
EET Emission Estimation Technique
EF Emission Factor
EFR Emission Factor Ratting
EPA Environment Protection Authority
ESP Electrostatic Precipitator
GF Generic Factor
INV Inventory
kW kilowatts
3
m Cubic meters
MSDS Material Safety Data Sheets
NEPM National Environment Protection Measure
NOI Notice of Intention
NOX Oxides of Nitrogen
NPI National Pollutant Inventory
PAH Polycyclic Aromatic Hydrocarbons
PM10 Particles which have an aerodynamic diameter equal to or less than 10
micrometers
SCAP Single Contact Acid Plant
SI Systeme Internationale
TSP Total Suspended Particulate
TSF Tailings Storage Facility
VOC Volatile Organic Carbons
US United States of America
US EPA United States Environmental Protection Agency
WA Western Australia

Zinc Concentrating, Smelting and Refining 74

12.0 References

12.1 References Cited

1. ANZSIC: Australian and New Zealand Standard Industrial Classification, Australian

Bureau of Statistics & NZ Dept of Statistics 1993, ABS Catalogue No 1292.0

2. Background Information for New Source Performance Standards: Primary Copper, Zinc and
Lead Smelters, Volume 1: Proposed Standards, EPA-450/2-74-002a, U. S. Environmental
Protection Agency, Research Triangle Park, NC, October 1974.

3. BPEMIM, Tailings Containment (1995), Best Practice Environmental Management in

Mining series, ’Tailings Containment’, EPA

4. EET Manual for Ferrous Foundries, National Pollutant Inventory, 1998

5. EET Manual for Fossil Fuel Electric Power Generators, National Pollutant Inventory 1999

6. EET Manual for Fuel and Organic Liquid Storage, National Pollutant Inventory, 1999

7. EET Manual for Mining, National Pollutant Inventory, 1999

8. EET Manual for Nickel Concentrating, Smelting and Refining, National Pollutant
Inventory, 1999

9. Ellis (1997), Investigation & Modelling of the Natural Decay of Cyanide in a Gold Mine
Tailings Pond, Daniel Ellis, Honours Thesis, University of Western Australia.

10. Encyclopædia of Chemical Technology, John Wiley and Sons, Inc. New York, NY, 1967.

11. G. Sallee, Personal Communication, Midwest Research Institute, Kansas City, MO.
June 1970. (as referenced in the Nickel EET Manual)

12. Heath et al (1998), A method for measuring HCN(g) emission from CIP / CIL tanks, CSIRO &
Curtin University

13. Industrial Process Profiles for Environmental Use, Chapter 28 Primary Zinc Industry, EPA-
600/2-80-169, U. S. Environmental Protection Agency, Cincinnati, OH, July 1980.

14. MERIWA Project M241 (1998), Saline Tailings Disposal & Decommissioning, Australian
Centre for Geomechanics [ACG : 1004-98 (A)/(B)]

15. Mt Keith Nickel (1996), Mt Keith Nickel Project Tailings Storage Upgrade CER, Jan 1996,
for WMC by Woodward Clyde

16. Particulate Pollutant System Study, Volume 1: Mass Emissions, APTD – 0743, U. S.
Environmental Protection Agency, Research Triangle Park, NC, May 1971.

Zinc Concentrating, Smelting and Refining 75

17. R. B. Jacko and D. W. Nevendorf, “Trace Metal Emission Test Results From A Number
Of Industrial And Municipal Point Sources”, Journal of the Air Pollution Control
Association, 27(10):989-994. October 1977

18. Simovic (1984), Report on Natural Degradation of Cyanides from the Cullaton Lake Gold
Mines Effluent, Environment Canada, Waste Water Technology Centre. NOTE:
Referenced through Ellis, 1997

19. Systems Study For Control of Emissions In the Primary Nonferrous Smelting Industry,
Volume 1, APDT-1280, U. S. Environmental Protection Agency, Research Triangle Park,
NC, June 1969.

20. Technical Guidance for Control of Industrial Process Fugitive Particulate Emissions, EPA-
450/3-77-010, U. S. Environmental Protection Agency, Research Triangle Park, NC,
March 1977.

21. Telephone conversation with ANCOLD representative, Re. Guidelines on Tailings

Disposal and TSFs seepage, NOTE Referenced in the Nickel EET Manual.

22. US EPA. June 1999. Emission Factor Documentation for AP-42, Section 12.7 Zinc Smelting.
United States Environmental Protection Agency, Office of Air Quality Planning and
Standards. Research Triangle Park, NC, USA.
http://www.epa.gov/ttn/chief/ap42.html

23. WMC Report Ref 692 634 (1992), Investigation of Engineering Design Criteria for Xanthate
Handling Facilities

12.2 References Not Cited

1. Hayes, P., Process Principles in Minerals and Materials Production, Hayes Publishing, Qld
1993

2. Linkson, P., Extractive Metallurgy Lecture Series, University of Sydney 1998

Zinc Concentrating, Smelting and Refining 76

Appendix A - Sources of Existing Data

Existing Data

The emission estimation methods proposed in this manual require best available data.
This data may be available within a corporation or facility in a range of forms, and sharing
data between facilities will aid reporting and allow for a greater level of accuracy in the
estimation of emissions.

The data may be used to:

• Directly estimate emissions;

• Provide guidance on the most appropriate estimation methods to be used; and
• Provide guidance on where direct monitoring may be most beneficially carried out.

Data sources may include the following:

A1 Existing Data & Research

Research projects of interest to industry are often sponsored, such as university Honours,
Master or PhD projects. These may be very directed areas of research, such as slag content
and leachability or hydrogeological contamination, and results may not be widely
available even within a facility, or may be held at a corporate level.

Some mine sites currently address their dust emissions as three distinct components:

• The monitoring of ambient dust levels:

• The assessment of dust sources by measurement, visual means or mass balance; and
• The implementation of dust control strategies.

This data may be applied to emission estimation methods to increase their accuracy either
directly through the development of emission factors or indirectly by identifying
additional processes within mass balances.

Processing sites may also have carried out discrete monitoring studies to determine the
health or environmental impacts of particular substances. While these studies may have
shown that minimal health or environmental risk is posed and hence ongoing monitoring
is not required, it may also be used to allow more accurate estimation of NPI substances.

Many sites will have access to geotechnical data and groundwater data for the processing
site from work carried out in the past (during exploration or when the refinery was built).
This data may provide information on groundwater flows, the location of palaeochannels
and other geological formations, and provide useful data for deciding the location and
depths of any monitoring boreholes.

Zinc Concentrating, Smelting and Refining 77

A2 Process Monitoring

Elements of the process may be monitored regularly in order to optimise recovery of the
product. This data may be applied to emission estimation methods such as mass balance,
serving as a verification of the mass balance to that stage of the process and raw data.

Monitored areas may include:

• Ore;
• Concentrate;
• Slag; and
• TSFs water input and return.

Monitoring may also be undertaken for environmental or health and safety requirements
and may include:

• Ammonia;
• Cyanide;
• Sulfur dioxide;
• Acids; and
• Carbon monoxide.

A3 Licences & Reporting

Smelters and refineries may be required to carry out monitoring that can be applied to the
requirements of the NPI. This data may include the following parameters:

• Sulfur dioxide;
• Carbon monoxide;
• Sulfuric acid fumes;
• Dust and particulates;
• Metals; including arsenic, selenium, antimony, beryllium, cadmium, lead, mercury,
chromium, manganese, cobalt, copper, nickel, and zinc;
• Chemical spills, including cyanide; and
• Dangerous goods licensing.

Facilities may monitor TSFs and storage ponds at regular intervals to ascertain reuse
potential and treatment methods such as neutralisation. Where seepage from ponds and
TSFs is suspected monitoring of bore holes may also be undertaken. Parameters may be
expressed as soluble or total, and may include:

• pH;
• Conductivity and TDS;
• Standing water level; and
• Metals.

Zinc Concentrating, Smelting and Refining 78

The data may be used:

• Directly where NPI substances are being monitored and reported;

• Indirectly such as dust monitoring where speciation of the dust component may be
required; and
• Relationally where the ratio of a monitored parameter can be related to the emissions
of an NPI substance.

A4 Approvals Data

Zinc smelters and refineries may have environmental assessment reports or other
approval documents, which contain a range of facility characterisation and operational
efficiency data. This information may be applied to emission estimation methods to
provide greater accuracy in reported data.

For example from March 1993 all proposals submitted to WA DoME require a detailed
summary and list of commitments. The range of information must be reported under the
guidelines (NOI Guidelines, 1993) including:

• Properties of TSFs;
• TSF construction parameters;
• Decant or under drainage systems;
• Liner type; and
• Monitoring.

A5 Regulatory Data

Regulatory and government departments may hold extensive data relating to individual
facilities, state and territories, or national and international sources. This data may be
accessed to provide a more extensive database of available information with which to
develop facility or corporate emission estimation strategies.

A6 Suppliers

Suppliers should be able to provide in-depth data regarding the fates of supplied
chemicals within the process.

A good example of this would be xanthates which breakdown to form carbon disulfide.
Suppliers may be able to provide data relating to the proportional breakdown of
xanthates, environmental stability and potential for carry through in the zinc process and
to TSFs.

Another example is sulfur content of fuel.

Zinc Concentrating, Smelting and Refining 79

A7 Inventory

A facility inventory may be used to identify all inputs to the zinc process and the usage
rates in relation to ore treated and product achieved. The inventory should be used as a
tool to assist in the estimating and reporting process and will not need to be submitted
with estimated emissions.

In addition to its use within the NPI framework a facility inventory may also be used to
determine material usage across the site assisting in:

• Financial planning;
• Resource planning;
• Waste minimisation; and
• Environmental reporting.

It is likely that most facilities will have an inventory of some type and reference to this
may enhance the accuracy of emission estimation and be applied to all emission
estimation methodologies.

Zinc Concentrating, Smelting and Refining 80

An example of an existing facility inventory is presented below.

Table A1 - Inventory of a Zinc Processing Facility

INPUTS Units Jan Feb Mar ... Dec TOTAL
Tonnes of ore treated tonnes
Zinc production kg
Sodium Cyanide tonnes
Quicklime (78% CaO) tonnes
(88% CaO) tonnes
3
Oxygen m
Carbon tonnes
Flocculent tonnes
Antiscalant tonnes
Diesel litres
Grinding balls tonnes
Electricity kWh
LP Gas tonnes
Caustic soda tonnes
Hydrochloric acid tonnes
Potable Water kl
Bore Water Total kl
Decant Water from
kl
TSFs
TSF dewatering system kl
TSF decant return kl
TSF underdrainage kl

Zinc Concentrating, Smelting and Refining 81