Professional Documents
Culture Documents
Note
FIRE ASSAYING
Art or Science?
The pyro-metallurgical recovery of gold from precious metal ores has been practiced for over
two thousand years. The basic fire assaying technique for the determination of gold has changed
little over the centuries. The only major scientific advance probably occurred in the early 1960s
with the introduction of atomic absorption spectroscopy (AAS). This provided an alternative to the
traditional and time consuming gravimetric technique for the determination of gold. There was
no change to the chemistry involved in fire assaying but AAS simply provided assayers with the
ability to process more samples and achieve lower detection limits. This was the beginning of the
high capacity fire assay facilities that we see operating today.
Commercial laboratories have made significant productivity advances over the past forty years to
keep pace with the demand for fire assay determinations. However the basic chemistry remains
the same. The nexus between productivity and chemistry is important as it explains many of the problems that geologists and
metallurgists experience when dealing with commercial fire assay data. Because gold is rarely homogeneously distributed in nature
and usually present in quite low concentrations, the frequent approach to fire assaying is to request the largest test sample possible
to obtain a more statistically valid result. Unfortunately, what charge weight is requested for assay and what can be realistically
analysed may bear little similarity. A basic knowledge of the chemistry and practice of fire assaying can be helpful in understanding
why this divergence may occur.
BASIC PRINCIPLES
The fire assay technique uses high temperature and flux to melt the rock and allow the gold
to be collected. Lead formed from the reduction of litharge (PbO), is traditionally used as the
collecting medium for silver and gold. The test sample is intimately mixed with a suitable flux
that will fuse at high temperature with the gangue minerals present in the sample to produce a
slag that is liquid at the fusion temperature. The liberated precious metals are scavenged by the
molten lead and gravitate to the bottom of the fusion crucible.
Upon cooling, the lead button is separated from the slag and processed in a separate furnace
for a high temperature oxidation (cupellation) where the lead is removed, leaving the precious
metals behind as a metallic bead called a prill. Traditionally this prill was then partially dissolved in nitric acid (parted) to remove silver
and the remaining gold determined by weighing (gravimetry). Alternatively, the prill can be dissolved in a mixture of hydrochloric
and nitric acid (aqua regia) and the concentration determined by spectroscopic methods (AAS, ICPAES or ICPMS). The concentration
is normally expressed as parts per million (ppm), which is equivalent to grams per tonne (g/t).
FLUXES
The following chemicals are normally found in, or added to, a commercial fire assay flux. Some of these re-agents play multiple
roles during fire assay, depending on the sample matrix being analysed. The flux composition may have to be supplemented by
increasing the proportion of one or more of these components to produce a successful fusion
REAGENT
REASONING
Litharge
Used to provide lead to collect the precious metals. It is also a strong basic flux and reacts with metallic
oxides and silica to form a slag. By far the most expensive component of a fire assay flux.
Soda Ash
A powerful basic flux that is usually the principal component of fire assay flux. It reacts with silicates to form
a slag.
Borax
An acidic flux that lowers the fusing point of all slags. It forms fusible complexes with limestone and magnesite
Silica
An acidic flux that forms the principal component of many samples. Small amounts are present in the flux to
prevent attack on the fire assay crucibles when assaying samples deficient in silica.
Nitre
A powerful oxidising agent added to the flux when assaying samples containing sulfides.
Flour
Silver
A small amount is added to the flux to provide a collection medium for the precious metals.
To cope with the ever increasing demand for gold assays, commercial laboratories have focused on increasing productivity through
the introduction of larger furnaces, mechanical sample/flux mixing equipment and multi-pour systems. This has resulted in the
standardisation of fire assay crucibles to a shape that allows efficient use of the furnace floor space. This, however, limits the ability
of the laboratory to increase the amount of flux used where the higher flux to sample ratio is required.
Most commercial laboratories recommend the use of a 30 gram fire assay charge weight as this provides the best compromise
between optimum gold recoveries and the potential for a poor fusion. ALS Minerals typically performs fire assay determinations
using a flux to sample ratio of 5 6:1 to reduce the chance of a poor fusion and the resulting low precious metal recoveries.
Clients requesting higher charge weights on the grounds that this will provide a more statistically valid sample may well find that
assay results on their internal QC samples will tend to have a negative bias, a bias that will be more pronounced when assaying a
difficult sample matrix. The more difficult the sample matrix, the greater the chance of a failed assay resulting in the laboratory
having to repeat the assay at its own cost. This, combined with the need to maintain efficient turnaround times, drives the laboratory
to always use its experience in estimating a fire assay charge weight that will maximise its chance of achieving a successful fusion.
DIFFICULT SAMPLES
There are a significant number of elements and compounds that create difficulties for fire
assayers. Some of these difficulties can be overcome by modifying the fire assay flux. In other
cases, the only available option is to reduce the charge weight to limit the amount of impurities
that can concentrate in the lead button. A brief list of the main offenders follows:
Procedures are available to successfully fire assay nearly all sample types provided the composition
of the material is known. Unfortunately, this knowledge is rarely available for a commercial
laboratory. Fire assayers must therefore hazard a guess at the composition and either modify
the flux, reduce the sample weight, or both. Accordingly, the failure rate for certain sample types
may initially be quite high, leading to re-assays and a delay in releasing the results.
ELEMENT
COMMENT
Copper
May be reduced to the metal during fusion and reports in the lead button. This can then inhibit cupellation, making it impossible to recover the precious metals. Alternatively, it may react with pyrite to form
a matte that will preferentially absorb gold.
Nickel
Reacts similarly to copper with regards to cupellation, but will create problems at far lower concentrations (> 0.5% in the lead button). A combination of nickel and copper will create far greater problems
than either of the elements individually.
Antimony
Completely miscible with molten lead. More than 2% antimony in the lead button may cause cracking of the cupel, resulting in low gold recovery. It will also form antimonides with copper, nickel or iron
(speiss) which will preferentially absorb gold.
Arsenic
Will form arsenides with copper, nickel or iron (speiss), resulting in low gold recovery.
Tellurium
Extremely detrimental to the recovery of precious metals during cupellation when present in amounts
of > 0.5% in the lead button. It lowers the surface tension of the precious metal prill, allowing some of
the dor to be absorbed by the cupel.
Selenium
Sulfur (Sulfides)
Can cause problems by forming mattes with copper, nickel or iron compounds, resulting in low gold
recoveries. Will also produce large lead buttons if using a high litharge flux. This can be controlled by
adding a calculated amount of oxidant.
Carbon (organic
matter)
Can cause major problems during fire assaying due to the formation of lead shot within the slag, leading to low lead button weights. This will result in low gold recoveries.
Another difficult sample type, but one that most geologists would love to have, are those that contain very high
concentrations of gold, but very little silver. The end result is a large precious metal prill that cannot be parted until
additional silver is added (inquarting) and the cupellation step repeated. High gold samples will also increase the risk of
contamination throughout the fire assay circuit.
SUMMARY
This brief description of fire assaying will hopefully provide customers with an understanding of the problems and pitfalls that exist
and why laboratories follow certain practices to obtain a satisfactory outcome. Fire assaying is not a simple materials handling
procedure that will always provide a satisfactory result just by following a recipe. There is a significant knowledge requirement that
can only be gained through many years of experience in handling the myriad of sample matrices that may contain gold.
Geochemistry
Metallurgy
Mine Site
Inspection
Coal
Asset Care
Tribology
Food&
Environmental Pharmaceutical