Paper Review of “Assessment of minerals and iron-bearing phases present in

hydrometallurgical residues from a nickel sulfide concentrate and availability of residue

associated metals”
A. Steel*, K. Hawboldt, F. Khan
Published on April 23, 2009
Submitted by: Shainodin Magondacan D.

Abstract
Hydrometallurgical facilities that refine nickel sulfide ores produce waste residues in the
form of sludges. These sludges contain various metals, along with iron and sulfur-bearing
minerals and compounds. Understanding the geochemical and mineralogical characteristics of
these residues is vital for effective industrial waste management. By using techniques like
Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD) analysis, it has been
observed that the minerals formed in the process primarily consist of gypsum, iron oxides such
as hematite and magnetite, iron hydroxides, and remaining sulfur and sulfides like FeS,
chalcopyrite, pyrrhotite, and pentlandite.
A distinctive framboidal structure is observed in the iron oxide particles within the leach residue,
and this structure is pertinent to how it interacts with metals during the leaching process. To gain
a better understanding, researchers compare the mineralogy and microstructure of residues from
a small-scale "mini plant" to those from a larger "demonstration plant" using SEM and XRD.
Furthermore, they employ sequential extractions to determine the connections between different
mineral phases and specific metals within each residue.
Introduction
Vale Inco Newfoundland and Labrador Limited (VINL) has experimented with an innovative
hydrometallurgical method to purify nickel, cobalt, and copper extracted from the nickel sulfide
concentrate originating from the Voisey's Bay mine site in Labrador, Canada. A demonstration plant was
in operation from 2005 to 2008, and the construction of a full-scale plant began in 2009. The
hydrometallurgical process for nickel not only eliminates SO2 emissions but also directs sulfur and minor
metal concentrations like nickel, copper, and cobalt into wastewater and process residue. Due to the
limited application of hydrometallurgy for processing nickel sulfide concentrate, detailed
characterization data about the process residue are scarce.
The ore from the Voisey's Bay mine comprises 70% pyrrhotite, 15% pentlandite, 10%
chalcopyrite, and 5% ilmenite. In the disseminated to semi-massive zone, 40% plagioclase or
olivine is present along with other accessory minerals. The typical VINL feed concentrate
analysis is outlined in Table 1. Within the VINL hydrometallurgical process, the concentrate
undergoes a chlorine pre-leach, followed by pressure oxidative leaching using hydrochloric acid
at 150 °C.
Given the high sulfur content in the residue, along with sulfur-bearing compounds and a small
percentage of unprocessed sulfide minerals, there is a potential for sulfur to oxidize, leading to
acid production and leaching of residual metals. This study focuses on mineralogical
characterization work and sequential extraction experiments performed on hydrometallurgical
residues from both the demonstration plant and the mini-plant, which are respectively at 1:100
and 1:1000 scales compared to the full-scale plant currently under construction. Understanding
the partitioning of metals and sulfur within iron-bearing phases and minerals present in the
residue, as well as the availability of these metals, will assist in predicting the functioning of the
full-scale plant's residue disposal system and the long-term requirements for residue stabilization.
Samples of hydrometallurgical residue were collected from test campaigns conducted at the
demonstration plant in Argentia, Newfoundland. The demonstration plant operated continuously
with variable feed conditions, while the mini-plant employed both batch and continuous feed
processes. The residues from these plants exist in the form of sludges and are generated through
precipitation processes or pressure leaching.
Two primary sources of sludges or residues are identified: Neutralized Leach Residue (NLR) and
Neutralized Gypsum Residue (NGR). The Neutralized Combined Residue (NCR) designated for
disposal at the full-scale plant consists of a mixture of approximately 55% NLR and 45% NGR,
with the pulp density adjusted to around 40% through the addition of wastewater.

Theoretical Background
Nickel sulfide concentrate typically contains high concentrations of sulfur and minor
metals such as nickel, copper, and cobalt. This novel hydrometallurgical process converts the
sulfur and these minor metals into wastewater and process residue. However, the characterization
of the process residue has been limited due to the relative novelty of the hydrometallurgical
approach for nickel sulfide processing.
Furthermore, the theoretical background includes information about the hydrometallurgical
residues, which are generated through either precipitation processes or pressure leaching,
resulting in sludges. Two key types of sludges are identified: Neutralized Leach Residue (NLR)
and Neutralized Gypsum Residue (NGR), with the combined residue for disposal (NCR) being a
mixture of these components.
This theoretical background also highlights the unique challenges and environmental
considerations in hydrometallurgical extraction processes, particularly regarding the removal of
iron from pregnant solutions to ensure stable disposal. Additionally, it emphasizes the
differences in mineralogy and chemical properties of hydrometallurgical residues compared to
traditional tailings, underlining the need for specialized characterization methods. Prior research
in the field of mineralogical characterization for similar materials and the findings from other
studies in this domain further contribute to the theoretical foundation.
Methodology
Advanced scientific instruments, including the FEI Quanta 400 scanning electron microscope
(SEM) with the JKMRC Mineral Liberation Analyzer (MLA) and the Rigaku Ru-200 12 kW
automated X-ray diffraction (XRD), were employed for a detailed analysis of the composition
and structure of iron-bearing substances and potential minerals within the residues.
The SEM allowed for precise spot analyses of individual particles to determine their elemental
content through generated spectra. In this process, many similar particles were analyzed before
selecting a representative spectrum. Additionally, area spectra were created to estimate the
average elemental content of the samples, ensuring reproducibility through multiple area spectra.
To determine the distribution of mineral groups and phases in the NCR and NLR samples, the
SEM's MLA software was used. Initial spot assessments of sample particles with varying
elemental compositions helped identify the primary mineral groups or phases for each particle
type. After numerous assessments, a select number of spectra were chosen to represent the
particles in the samples. These spectra were then incorporated into the MLA database, and the
MLA software was used to calculate the quantity and distribution of each mineral group or phase
in the samples.
In this study, the terms "phases" or "iron-bearing phases" refer to poorly crystalline or
amorphous minerals found in the residues. The primary residue minerals, whether crystalline or
amorphous, include gypsum, iron hydroxide, and iron oxide, along with residual sulfur and
sulfides like FeS, chalcopyrite, pyrrhotite, and pentlandite. All of these, except the metal
sulfides, are secondary minerals formed during leaching and precipitation processes. FeS, an iron
sulfide phase identified by the SEM, primarily consists of iron and sulfur with minimal oxygen.
This amorphous form, similar to pyrite or mackinawite, may resemble the FeS precipitate
described in earlier studies.
Sequential extractions were carried out on the NGR, NLR, and NCR samples to understand the
association of metals with specific mineral phases. The chosen method involved a five-step
extraction process used for speciating particulate trace metals. Details about each step's
dissolution of minerals or phases, as well as the specific extraction solutions and target minerals
for each step, can be found in reference materials. The use of sequential extractions in
hydrometallurgical residue analysis, while not widely reported, is believed to aid in
comprehending how metals linked to the residues are released and distributed among various
phases and minerals.
Results and Discussion

The SEM images revealed that the demonstration plant NGR consists of needle-shaped
gypsum particles and smaller iron hydroxide particles. Notably, the mini-plant NGR had larger
gypsum particles, likely due to longer mixing times, and more intense gypsum peaks in XRD
analysis. The iron removal process in hydrometallurgy presents advantages and disadvantages,
with difficulties in identifying specific iron hydroxides in small particle sizes. It's known that
hydrometallurgical residues often contain ferrihydrite and goethite, with potential matches for
the non-gypsum peaks in the NGR being ferrihydrite and goethite. Minor quantities of nickel and
copper, in various forms, were also detected. Metal adsorption on iron hydroxides is a
documented phenomenon and may explain the presence of metals in the NGR. Therefore, the
NGR likely contains goethite and ferrihydrite with adsorbed metals, as confirmed by previous
studies.
Notably, the SEM and optical microscopic examinations also revealed the presence of
unreacted sulfide ore minerals (pyrite, pyrrhotite, and pentlandite) alongside iron oxide particles
in the demonstration plant NGR. Larger particles, such as plagioclase, albite, or amphibole, were
also observed in the mini-plant leach residue. The NLR predominantly contains sulfur after iron
oxides, with unique spherical amorphous iron oxide particles that exhibit a framboidal structure.
Although there were suggestions of sulfur or residual pentlandite inside hollow iron oxide
particles, this was not confirmed in this study.

In summary, the sequential extractions of specific metals in the study showed distinct
trends in metal availability among different residues. Metals in the NGR exhibited higher
availability compared to the NLR, where the majority of metals were tightly bound to the
extraction residue, indicating lower leachability. Generally, metal concentrations were highest in
the NLR, followed by the NCR, and lowest in the NGR.

Conclusion:
In essence, the SEM and XRD analyses revealed important insights into the mineral
composition of the hydrometallurgical residue, helping us understand its behavior during
disposal. The NLR primarily consists of tiny spherical framboidal particles, primarily made of
iron, with varying amounts of oxygen, calcium, and sulfur. SEM analysis identified 16 different
phases in the NLR, including Fe-S phases, pure sulfur, and various Fe-O phases. XRD analysis,
while not capturing the amorphous minerals in the NLR, indicated the main minerals were
hematite, sulfur, and pyrite.
For the NGR, SEM work clearly displayed two particle types: gypsum and a small percentage of
an iron-bearing mineral. XRD analysis confirmed the presence of gypsum, potential iron
hydroxides, and other metal-bearing compounds. SEM and XRD findings revealed that both the
mini-plant and demonstration plant residues had similar microstructures and compositions, with
differences in gypsum percentages. This suggests that the mini-plant residue can represent the
larger plant residue for weathering and treatment studies.
The results of the five-step sequential extraction indicated that metals were more accessible in
the NGR than in the NLR. Hematite (iron) in the NLR is highly stable, whereas in the NGR, it is
less stable (iron hydroxides). Trace metals like nickel, copper, cobalt, and zinc are linked not
only to hematite in the NLR but also with other minerals or phases, making a significant portion
of these metals more prone to weathering.
For the treatment and disposal of these residues, it's crucial to consider the metals associated with
all phases present, particularly those susceptible to weathering. This study offers preliminary
information about the microstructure, mineralogy, and stability of trace metals in these residues,
with further research needed to validate these results and understand the weathering properties of
sulfur-bearing phases, especially in the NLR.

Critique by Peer-reviewer
The research offers vavaluable insights into the mineralogical characteristics of
hydrometallurgical residues and their potential implications for disposal and treatment. However,
there are several points that could benefit from further clarification and improvement:
1. Limited Context: While the text mentions various minerals and phases, it does not offer a
broader context or comparison to standard or expected values in similar
hydrometallurgical processes. Such context would help readers understand the
significance of the findings.
2. Absence of Methodological Details: The text briefly mentions SEM and XRD analyses
but does not provide adequate details about the specific methods and techniques used. A
more thorough description of the analytical procedures would be beneficial for
transparency and reproducibility.
3. Unclear Significance of Variations: The text mentions variations in gypsum percentages
between the mini-plant and demonstration plant residues but does not explain the
potential implications or significance of these variations.
4. Need for Further Study: The conclusion rightly acknowledges that further research is
required to confirm the results and understand the weathering properties of sulfur-bearing
phases. However, it would be beneficial to outline specific areas or questions that future
studies should address.
5. Lack of Discussion on Environmental Impact: The text primarily focuses on the
mineralogical aspects of the residues but does not delve into the potential environmental
impact of these findings. Discussing the implications for environmental management and
disposal strategies would make the research more practical and applicable.
In summary, while the information provided is a good starting point, addressing these points
would strengthen the research and make it more informative and useful for readers interested in
the field of hydrometallurgy and waste management.