minerals

Article
Weathering of Ophiolite Remnant and Formation of
Ni Laterite in a Strong Uplifted Tectonic Region
(Yuanjiang, Southwest China)
Wei Fu 1,2, * , Yangyang Feng 1 , Peng Luo 1 , Yinmeng Zhang 1 , Xiaorong Huang 1 ,
Xiangwei Zeng 1 , Qian Cai 1 and Yongzhang Zhou 2
1 Guangxi Key Laboratory of Hidden Metallic Ore Deposits Exploration, Guilin University of Technology,
Guilin 541004, China; fengyangyang1021@163.com (Y.F.); pluo765@163.com (P.L.);
zhangyinmeng9312@163.com (Y.Z.); hxrong30@163.com (X.H.); samwayzeng@163.com (X.Z.);
caiqian7788@163.com (Q.C.)
2 Center for Earth Environment & Resources, Sun Yat-sen University, Guangzhou 510275, China;
zhouyz@sysu.edu.cn
* Correspondence: fuwei@glut.edu.cn; Tel./Fax: +86-0773-5897019




Received: 30 November 2018; Accepted: 10 January 2019; Published: 16 January 2019


Abstract: The Yuanjiang Ni deposit in southwestern margin of the Yunnan Plateau is the only
economically important lateritic Ni deposit in China. It contains 21.2 Mt ore with an average grade
of 1.05 wt % Ni and has been recognized as the second largest Ni producer in China following the
Jinchuan super-large magmatic Ni–Cu deposit. This Ni deposit is hosted within the lateritic regolith
derived from serpentinite within the regional Paleo-Tethyan Ophiolite remnants. Local landscape
controls the distribution of the Ni mineralized regolith, and spatially it is characterized by developing
on several stepped planation surfaces. Three types of lateritic Ni ores are identified based on
Ni-hosting minerals, namely oxide ore, oxide-silicate mixed ore and silicate ore. In the dominant
silicate ore, two phyllosilicate minerals (serpentine and talc) are the Ni-host minerals. Their Ni
compositions, however, are remarkably different. Serpentine (0.34–1.2 wt % Ni) has a higher Ni
concentration than talc (0.18–0.26 wt % Ni), indicating that the serpentine is more significantly
enriched in Ni during weathering process compared to talc. This explains why talc veining reduces
Ni grade. The geochemical index (S/SAF value = 0.33–0.81, UMIA values = 17–60) indicates that the
serpentinite-derived regolith has experienced, at least, weak to moderate lateritization. Based on
several lines of paleoclimate evidence, the history of lateritization at Yuanjiang area probably dates
to the Oligocene-Miocene boundary and has extended to the present. With a hydrology-controlled
lateritization process ongoing, continuous operation of Ni migration from the serpentinite-forming
minerals to weathered minerals (goethite and serpentine) gave rise to the development of three types
of Ni ore in the regolith. Notably, the formation and preservation of the Yuanjiang lateritic Ni deposit
has been strongly impacted by regional multi-staged tectonic uplift during the development of
Yunnan Plateau. This active tectonic setting has promoted weathering of serpentinite and supergene
Ni enrichment, but is also responsible for its partial erosion.

Keywords: lateritic Ni deposit; lateritization process; serpentine; paleoclimate; tectonic uplift; China

1. Introduction
Chemical weathering of ultramafic rocks has produced numerous lateritic profiles and associated
Ni deposits, as best illustrated by those in New Caledonia, Cuba, Philippines, Indonesia, Colombia,
Australia, and Brazil [1,2]. These deposits, commonly termed as lateritic Ni deposits, account for
60%–70% of the world’s nickel resource and nearly 60% of the annual global nickel production [3].

Minerals 2019, 9, 51; doi:10.3390/min9010051 www.mdpi.com/journal/minerals

Minerals 2019, 9, 51 2 of 25

They are mostly situated in equatorial latitudes characterized by warm and humid tropical climate at
present or ancient time. Genetically, it is associated with obducted ophiolite complexes in accretionary
belts or komatiites and layered ultramafic rocks in stable cratonic blocks [4,5]. In the last two decades,
lateritic Ni deposit have received increasing attention in both the economic geology and exploration
communities [6–18], largely due to the development of metallurgical technology for lateritic Ni ores
and the shortage of sulfide Ni resources [19]. Ni laterites are also considered worthy targets for critical
metals (REE, Sc, PGE, etc.) exploration [20].
Previous studies have significantly advanced our understanding in the nature and origin of
lateritic Ni deposits: (1) Based on the dominant Ni-hosting minerals, lateritic Ni deposits can be
divided into the oxides, hydrous Mg silicates and clay silicates subtypes. Such a subdivision is of
economic importance in terms of resource evaluation and mineral processing [3,6]. (2) Large vertical
variation in mineralogy and geochemistry of Ni-rich laterite profiles record the complex lateritization
history of ultramafic rocks [7,21]. (3) Supergene Ni enrichment (in some case accompanied by Co
enrichment) can be summarized as a eluviation-illuviation effect, which generated a significant
change in Ni concentration, Ni speciation and even Ni isotope in the rock–regolith system [3,22–24].
(4) Formation of Ni-rich secondary minerals at atmospheric pressure and temperature is ascribed
to a series of supergene processes regulated by water–rock interaction with lateritization ongoing,
including sorption, substitution, dissolution/precipitation, etc. [18,21,25]. (5) Mode of occurrence
of the lateritic Ni deposits are controlled by a combination of geological, climatic, topographic, and
hydrologic parameters [4,5,7], especially the importance of topographic-hydrologic controlling on
its ore grade is highly concerned in recent studies [25–27]. (6) Some lateritic deposits may have
been products of multiphase chemical weathering, and their preservation reflects balance between
weathering and erosion [3,15,21]. Despite the general understanding in the formation and genesis of
lateritic Ni deposits, details on processes and evolution of supergene Ni enrichment remain enigmatic
due to the complex parent rock lithologies and local environmental conditions.
Several lateritic Ni deposits have been discovered in China, including the Yuanjiang [28],
Malipo deposits in Yunnan Province and the Chaiziyuan deposit in Sichuan Province [29], which are
tectonically located along the Tethyan ophiolite belts in Southwest China. These lateritic Ni deposits
have been explored and mined for more than 40 years, but little research has been published. In this
paper, we present the geological, mineralogical and geochemical data of the Yuanjiang deposit.
The results are used to provide insights into the formation and evolution of the Yuanjiang deposit,
which in turn help build a genetic model in the context of regional geological evolution.

2. Geological and Geographical Setting

The Yuanjiang deposit is located in the southwestern portion of Yuanjiang county, Yunnan Province,
Southwest China (Figure 1a). Tectonically, it is within the Ailaoshan suture, which marks the closure of
the Ailaoshan ocean basin and subsequent late Triassic collision of the Yangtze plate in the northeast
and the Simao-Indosinian plate in the southwest [30,31]. Ultramafic bodies occur as isolated exposures
in this tectonic belt, and they have been interpreted to be a part of the Ailaoshan ophiolite complex that
extends for >300 km along a NW–SE strike [32]. The main ultramafic bodies include, from north to
south, Bailadu, Jinchang, Anding, Longtan, Mengli and Midi (Figure 1b). These ultramafic bodies are
lithologically dominated by lherzolite, harzburgite, or peridotite, with variable serpentine alteration [33].
Other exposed geological units include the Permian to Triassic marine sedimentary rocks,
the Ailaoshan metamorphic belt and unconsolidated Quaternary sediments [34]. The Permian to
Triassic sequences are mainly composed of sandstones, conglomerates, mudstones, and intercalated
shales, which are variably intruded by the ultramafic bodies and subjected to sub greenschist facies
metamorphism in places where they were intruded by the intrusive rocks. The Ailaoshan metamorphic
belt occurs to the north of the ophiolite complex and consists of granitic gneiss, quartz-feldspar-biotite
gneiss, quartz-mica schist and banded marble. Quaternary sediments are limited to some terrestrial
basins or low relief upland landscapes and consist of unconsolidated sandstones and conglomerates.
Minerals 2019, 9, 51 3 of 25

The mining area is situated near the Tropic of Cancer (23.5◦ N) and currently has a subtropical
climate,Thewithmining area is situated
an average near the Tropic
yearly precipitation of Cancer
more (23.5°
than 1600 mmN)and
and acurrently has a subtropical
mean annual temperature
climate, ◦ with an average yearly precipitation more than 1600 mm and a mean
of 18–20 C. Local geomorphology is a part of the Yunnan plateau on the southeastern marginannual temperature of of
18–20 °C. Local geomorphology is a part of the Yunnan plateau on the southeastern
the Tibetan Plateau, consisting of hummocky mountains, ridges and intermountain basins. At least margin of the
sixTibetan
planation Plateau, consisting
surfaces, whichof hummocky
are distributed mountains, ridges
in a vertical andofintermountain
extent basins.1700
ca. 400 m between At least
and six
2100
planation surfaces, which are distributed in a vertical extent of ca. 400 m between 1700
m, have been identified within the ore district and surrounding areas. Such a stepped topographic and 2100 m,
have been identified within the ore district and surrounding areas. Such a stepped topographic
feature has also been reported in other areas of the Yunnan plateau and is interpreted to reflect a staged
feature has also been reported in other areas of the Yunnan plateau and is interpreted to reflect a staged
uplift and episodic erosion history [35,36]. The planation surfaces are variably mantled by lateritic
uplift and episodic erosion history [35,36]. The planation surfaces are variably mantled by lateritic profiles
profiles with a few tens of meters thickness, and the lateritic regolith is commonly disconnected by
with a few tens of meters thickness, and the lateritic regolith is commonly disconnected by local drainage
local drainage incision.
incision.

Figure
Figure 1. Simplified
1. Simplified geological
geological map
map ofof the
the Yuanjiang
Yuanjiang region,
region, Yunnan
Yunnan Province,SW
Province, SWChina,
China,showing
showingthe
the location (a) and main geological context (b) of the study
location (a) and main geological context (b) of the study area. area.

3. Geology
3. Geology ofof the
the YuanjiangDeposit
Yuanjiang Depositand
andProfile
ProfileDescription
Description
The
The Yuanjiang
Yuanjiang depositisisthe
deposit thelargest
largestlateritic
lateritic Ni
Ni deposit inin China
Chinawith
withproven
provenreserves
reservesofof
21.2 MtMt
21.2
at >at1.05
> 1.05 wtNi,
wt % % and
Ni, and it represents
it also also represents the second
the second largestlargest Ni producer
Ni producer in China in following
China following the
the Jinchuan
Jinchuan magmatic
super-large super-large magmatic
Ni–Cu Ni–Cu
deposit. This deposit. This deposit
deposit contains six orecontains
districts:six ore districts:
Bailadu, Bailadu,
Jinchang, Anding,
Jinchang, Anding, Longtan, Mengli and Midi. These ore districts are scattered along
Longtan, Mengli and Midi. These ore districts are scattered along the Ailaoshan ophiolite belt and are the Ailaoshan
ophiolite
spatially belt and
related are spatially
to different relatedremnants.
ophiolite to different ophiolite
Among remnants.
them, Among
the Anding andthem, the Anding
Jinchang and
ore districts
Jinchang ore districts are the main mining parts of the whole deposit. The Jinchang ore district is
Minerals 2019, 9, 51 4 of 25

are the main mining parts of the whole deposit. The Jinchang ore district is located within the outcrop
area of the Jinchang ultramafic body, which is 15.6 km long and 0.4–1.93 km wide. The Anding ore
district is located to the southeast of the Jinchang ore district, where the Anding ultramafic body is
exposed in an area 7.2 km long and 0.3–0.8 km wide. Approximately 20–50% of the ultramafic bodies
are covered with regolith, which provide the host of lateritic Ni ore.
Nickel mineralized lateritic profiles are mainly distributed in the third (Figure 2a) and fourth
planation surfaces at altitudes of 1850–1860 m and 1920–1940 m, respectively. They have variable
thickness, mostly ranging from 6 to 13 m but locally exceeding 40 m (Figure 3a). The thickness of
weathering profiles reflects a combined effect of multiple factors such as lithologies of parent rocks,
fracture intensity, local geomorphological features, and recent erosion. Weathering profiles developed
on flat hilltops and low-lying plains are generally thicker than those on steep slopes and high-elevation
ridges. In areas where fractures or joints are particularly developed, weathering profiles may become
unusually thick due to preferential downward propagation of weathering front along more permeable
zones. Weathering profiles on high-elevation ridges and steep slopes have been significantly eroded,
with the bedrock or saprolite exposed at the present surface (Figure 2h). The parent lithologies are
dominated by massive serpentinite (Figure 2i), which are locally overprinted with talc and calcite veins.
The lateritic weathering profile is typically divided into two main horizons according to variations
in color, texture and mineral composition: the saprolitic zone at lower part and the limonitic zone
at upper part (Figure 3b). The saprolite is most developed in flat planation surfaces with thickness
from 6 to 20 m. It is overlying the serpentinite and generally has an irregular and transitional contact.
This zone is typically yellowish-brown, grayish-yellow or grayish-green in color and shows porous,
friable and heterogranular textures (Figure 2e). Many serpentinite relicts may occur at the lower part of
saprolite (Figure 2g), and original parent rock textures are partly preserved as well. The silicate minerals
(serpentine and talc) are the dominant components of the saprolite. More specifically, two types of
saprolite can be further discriminated in this zone, termed as the green saprolite occurring in the lower
part and the brown saprolite occurring in the upper part. The brown-saprolite contains a small amount
of Fe-oxyhydroxides and its texture seems earthier compared to the green saprolite. The limonitic zone,
mostly 2–10 m in thickness, is developed immediately above the saprolite. The contact between the two
zones is clear and can be readily recognized by their contrasting color, texture and mineral compositions
(Figure 2b). It is typically brownish-red to brownish-yellow, soft, porous, and fine-grained (Figure 2c).
Original parent rock textures have almost disappeared in this position. The mineralogy of this horizon
is dominated by Fe-oxyhydroxides with minor silicate or heavy minerals. Two sub-units can be
further divided, lower brown limonite and upper red limonite, which reflect their somewhat different
mineral or chemical compositions, as described below. In addition, small amount of hard ferruginous
concretions, with diameters of a few to several tens of mm, can be observed within the limonite locally.
To the top of the profile, the limonitic zone is variably covered by alluvial or other transported deposits.
This cover is yellow-brown and mainly composed of sandy clay, with scattered gravels of ultramafic
rocks or clastic rocks from adjacent sedimentary sequence.
Nickel mineralization is mainly concentrated in the lower part of the limonitic zone and the
middle to upper part of the saprolite. According to mine geologists, the Ni ore can be generally
sub-divided into three types based on the relative concentrations of Fe and Mg:

I: Ferruginous ore (Figure 2d) in the brown limonite: 0.5–1.3 wt % Ni; <10 wt % Mg; ~24 wt % Fe.
II: Ferruginous-magnesian ore (Figure 2d) in the brown saprolite: 0.5–1.6 wt % Ni; 10–20 wt % Mg;
11–13% wt % Fe.
III: Magnesian ore (Figure 2e) in the green saprolite: 0.2–1.3 wt % Ni; >20 wt % Mg; 8–11 wt % Fe.

The magnesian ores account for the majority of total reserve and production. According to the
general classification for lateritic Ni ore [4], the ferruginous and magnesian ores in the Yuanjiang
deposit broadly correspond to the oxide and silicate ores, respectively, with the ferruginous-magnesian
ore is mixed oxide-silicate ore.
Minerals 2019, 9, 51 5 of 25

Figure
Figure 2. 2. Macrophotographsof
Macrophotographs ofthe
thelateritic
lateritic Ni
Ni profile
profile at
at the
the Yuanjiang
Yuanjiangarea,
area,showing
showingitsitsfield
fieldgeological
geological
characteristics: (a) lateritic regolith at the Ⅲ-level denudation plane; (b) a typical
characteristics: (a) lateritic regolith at the III-level denudation plane; (b) a typical lateritic lateritic NiNi
profile
profile
showing the divided regolith units; (c) the boundary of red limonite and brown limonite;
showing the divided regolith units; (c) the boundary of red limonite and brown limonite; (d) the (d) the boundary
of brownoflimonite
boundary brownand brownand
limonite saprolite;
brown(e)saprolite;
the pale green saprolite
(e) the developed
pale green in the
saprolite middle and
developed inlower part
the middle
of the profile; (f) the residual talc-vein in the saprolite horizon; (g) a typical rocky saprolite showing a black
and lower part of the profile; (f) the residual talc-vein in the saprolite horizon; (g) a typical rocky
bedrock core surrounded by green saprolite; (h) outcrop of the bedrock exposed by mining; and (i) fresh
saprolite showing a black bedrock core surrounded by green saprolite; (h) outcrop of the bedrock
serpentinite in the bedrock.
exposed by mining; and (i) fresh serpentinite in the bedrock.
 Minerals 2019, 9, 51 6 of 25

Figure
Figure 3. The
3. The typical long cross-section
(a)(a) and vertical column (b)
ofofof the Ni laterite profile from the
Figure 3. typical long
The typical cross-section
long cross-section and
(a) vertical
and column
vertical column (b)(b) thetheNi
Nilaterite
lateriteprofile
profile from
from the
the
study
study sitesite at the
atsite
the Yuanjiang area, includingthethe locationofof
thethe samples.
study atYuanjiang area,
the Yuanjiang including
area, including location
the location of samples.
the samples.
Overall, the Yuanjiang Ni-bearing lateritic profile is characterized by a thick saprolite horizon as
Overall, the Yuanjiang
Overall, the Yuanjiang Ni-bearing lateritic profile is is
characterized
characterizedby a thick
thicksaprolite horizon as as
the main regolith unit and an Ni-bearing
abundancelateritic profile
of silicate ore as the main typeby ofathe Ni saprolite
ore. Thishorizon
is similar to
the main regolith
the main unitunit
regolith andandan abundance
an abundance of silicate oreore
of silicate as as
thethemain
maintype
typeofofthe
theNiNiore.
ore.This
This is
is similar
similar to
other hydrous Mg silicate lateritic Ni deposits, for example the Sorowako deposit in Indonesia [37],
otherother
hydrous Mg silicate
hydrous lateritic
Mg silicate Ni deposits,
lateritic Ni deposits,forfor
example
example thethe
Sorowako
Sorowakodeposit
depositin inIndonesia
Indonesia [37],
[37], the
the Cerro Matoso S. A. deposit in Colombia [6], and other cases worldwide (Figure 4). Therefore, the
CerroCerro
Matoso S. A.S.deposit
Matoso A. depositin Colombia
in Colombia [6],[6],
andandother
other cases
casesworldwide
worldwide(Figure (Figure4). 4). Therefore,
Therefore, the
Yuanjiang deposit can be considered as the hydrous Mg silicate type. Comparatively, the ore grade
Yuanjiang
Yuanjiang deposit
deposit can can be considered
be considered as the
as the hydrous
hydrous Mg Mg silicatetype.
silicate type.Comparatively,
Comparatively, the the ore
ore grade
of the Yuanjiang deposit (mean 1.05 wt % Ni) is relatively lower than most hydrous Mg silicate Ni
of the Yuanjiang deposit (mean 1.05 wt % Ni) is relatively lower than most hydrous Mg silicate Ni
of the Yuanjiang deposit (mean 1.05 wt % Ni) is relatively lower than most hydrous Mg silicate
deposits (mean 1.53 wt % Ni), possibly because of the absence of high grade garnierite ore. The so-called
deposits
deposits (mean(mean
1.53 1.53
wt %wtNi),
% Ni), possibly
possibly because
because of the
of the absence
absence ofof highgrade
high gradegarnierite
garnieriteore ore..The
The so-called
so-called
garnierite
garnieriteore
oreis is
defined
defined asasa amixture
mixture ofofneoformed
neoformed hydrous
hydrous Mg–Nisilicates
Mg–Ni silicateswith
withdistinctive
distinctive green
green
garnierite ore is defined as a mixture of neoformed hydrous Mg–Ni silicates with distinctive green
color, poor crystallinity and high Ni contents (up to 30–40 wt % Ni), as reported in many hydrous
hydrousMg
color,color,
poorpoor crystallinity
crystallinity andandhigh high
Ni Ni contents
contents (up(upto to 30–40
30–40 wtwt%%Ni),Ni),asasreported
reportedin in many
many hydrous
silicate type
Mg silicate Ni laterites [10,23,24,38]. However, the garnierite ore does not always exist in
exist hydrous
the
Mg silicate typetype Ni laterites
Ni laterites [10,23,24,38].
[10,23,24,38]. However,
However, thethe garnieriteore
garnierite oredoes
doesnotnotalways
always exist in the
in the
Mghydrous
silicate Mg
Ni deposits,
silicate Nisuch as in such
deposits, the case
as inoftheRiddle
case of inRiddle
Oregon, USA [39].
in Oregon, USA [39].
hydrous Mg silicate Ni deposits, such as in the case of Riddle in Oregon, USA [39].

Figure
Figure 4. 4.Comparison
Comparison of of the
the Yuanjiang
Yuanjianglateritic
lateriticNiNiprofile with
profile other
with typical
other silicate-type
typical lateritic
silicate-type Ni
lateritic
profiles
Ni profiles around the
around the world,
world, including
including the Soroako
the Ni
Soroako profile in Indonesia [40], Falcondo profile in
Figure 4. Comparison of the Yuanjiang lateritic profileprofile in Indonesia
with other [40], Falcondo
typical silicate-type profile
lateritic Ni in
Dominica
Dominica [9,41],
[9,41], and Cerro Matoso profile in Colombia [6]. The dotted lines show the boundaries of
profiles around theand Cerroincluding
world, Matoso profile in Colombia
the Soroako [6].inThe
profile dotted lines
Indonesia [40],show the boundaries
Falcondo profile in of
the saprolite
the saprolite horizons hosted silicate ore within the lateritic profiles from different sites.
Dominica [9,41],horizons
and Cerrohosted silicate
Matoso ore within
profile the lateritic
in Colombia [6]. Theprofiles
dottedfrom
linesdifferent
show the sites.
boundaries of
the saprolite
4. Samples and horizons hosted silicate ore within the lateritic profiles from different sites.
Analytical
4. Samples and AnalyticalMethods
Methods

One
4. Samples One
andideal
ideal sitesite
forfor
Analytical detailed
detailed
Methods regolith
regolith profile
profile study
study was
was selected
selected within
within thethe
main
mainmining
miningarea
areaofofthe
Jinchang ore district.
the Jinchang It is. It
ore district a continuous andand
is a continuous thick section
thick sectionwith
withaavertical
vertical extent ofca.
extent of ca.1010mm (Figure
(Figure 3a,b),
3a,b),
One ideal
reflecting
site for detailed regolith profile study was selected with in the main mining area of
reflecting thethemost
mostrepresentative
representative features
features of
of the lateritic
lateritic Ni
Ni profile
profileininthe
theregion.
region.Sampling
Sampling was
was
the Jinchang ore district. It is a continuous and thick section with a vertical extent of ca. 10 m (Figure 3a,b),
reflecting the most representative features of the lateritic Ni profile in the region. Sampling was
Minerals 2019, 9, 51 7 of 25

conducted orderly from the fresh parent rock through the saprolite zone and limonite zone to the
alluvial cover, as shown in Figure 3b. To ensure the representativeness of samples, all samples were
collected by similar volume standard of 1000 cm3 . Totally, 11 samples were collected for laboratory
analyses, including one parent rock sample (sample J-1), 7 saprolite samples (samples J-3, P1 -2, P1 -5,
P1 -7, P1 -9, P1 -11 and P1 -13), 2 limonitic samples (P1 -16 and P1 -18), and an alluvial sample (P1 -19).
Prior to laboratory analyses, all samples were naturally dried, and then each sample was divided
into several parts for different examinations. Original samples were used to analyze the bulk density.
Standard double-polished thin sections were prepared for examinations using optical microscopy and
electron microprobe analysis (EMPA). Powdered samples of 200 meshes were analyzed using X-ray
diffraction (XRD) and bulk geochemical techniques.
The bulk density was determined applying the traditional wax sealing method. Firstly, small
fragment of the hard rock or regolith sample were picked and weighed using electronic scale. Next,
the sample was dipped into melted max at 80 ◦ C for several minutes, making the surface of sample
totally coated by max. Then, the wax-sealed sample was put into the measuring cylinder with water
to get the volume data of the sample. Finally the bulk density was calculated as a function of weight
and volume.
X-ray diffraction data were acquired using a Philips X’ Pert MPD diffractometer equipped with a
Cu target tube, working at 40 kV and 40 mA. The range of 2θ scanning was from 5◦ to 80◦ . Scan step
and step duration were 0.05◦ and 3 s, respectively. Standard grinding and mounting of the sample
were performed prior to XRD analysis.
Whole-rock samples for geochemical analyses were dried at 70 ◦ C and then crushed and
powdered in an agate mill. The powder was further heated at 105 ◦ C to remove adsorbed water
before analysis. Major elements (Si, Al, Ca, Fe, K, Mg, Mn, Na, Ni and P) were measured using a
Rigaku X-ray fluorescence spectrometer (XRF). The accuracies of the XRF analyses are estimated to be
~2% (relative) for elements oxides with concentrations greater than 2 wt %, and ~5% for those present
in concentrations greater than 0.1 wt %. The detection limits for the major elements are generally better
than 30 mg/kg. For trace elements (Sc, Ti, V, Co, Cu, Zn, Ge, Rb, Sr, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th and
U) analysis, the samples were first digested by an HNO3 + HF acid mixture in high-pressure bombs,
and then measured using a Perkin-Elmer Elan 6000 ICP-MS with detection limits of about 10 µg/kg in
solid samples for trace elements. The precision of ICP-MS analyses is estimated to be better than 5%
(relative) for most trace elements with concentrations greater than 10 mg/kg and ~10% for elements
less than 10 mg/kg.
Electron microprobe analyses were made using a JXA-8230 electron microprobe attached with a
wavelength dispersive system. The measurement conditions were 20 kV accelerating voltage, 15 nA
probe current, and 2 µm beam diameter. Calibrations were performed using natural and synthetic
reference materials: forsterite (Mg, Fe, and Si), anorthite (Ca), albite (Na and, Al), chromite (Cr),
phlogopite (K), rutile (Ti), NiO (Ni), CoO (Co), and MnO (Mn). Back-scattered electron images and
elemental X-ray maps of Fe, Mg, and Ni were made at 15 keV and 10 nA.
Some laboratory work, including petrography, XRD and EMPA, was conducted in the Key
Laboratory of the Guangxi Hidden Metallic Ore Deposits Exploration in China, and the rest (whole-rock
geochemical analyses) was carried out in the Key Laboratory of Geochronology and Geochemistry,
Chinese Academy of Sciences.

5. Results

5.1. Bulk Density and Mineralogy

Bulk density is an important physical parameter of the lateritic Ni ore as it is required for industrial
utilization and ore genesis study. In the profile studied, the bulk density decreases from 2.455 g/cm3
in the fresh serpentinite to 1.196–1.672 g/cm3 in the saprolite and 0.851–1.094 g/cm3 in the limonite.
These values are comparable to other reported examples of ultramafic rocks regolith [42].
Minerals 2019, 9, 51 8 of 25

Petrographic observations show that the parent rock is mineralogically dominated by serpentine,
which is characterized by a fibrous or laminar crystal shape with pale to white color under
transmitted-light microscopy (Figure 5a,b). Minor primary minerals include pyroxene
Minerals 2019, 9, x FOR PEER REVIEW
(mainly
8 of 25
clinopyroxene), magnetite and olivine. Most of them are isolated or enveloped by serpentine veins,
forming a typical mesh-like
transmitted-light microscopystructure
(Figure(Figure 5a). The
5a,b). Minor amounts
primary of pyroxene
minerals and olivine
include pyroxene account
(mainly
clinopyroxene),
for less than 10% ofmagnetite and olivine.
total primary Most indicating
minerals, of them are strong
isolatedserpentinization
or enveloped by serpentine veins,rocks.
of the parent
Fine forming
veins ofatalctypicalaremesh-like structure (Figure
locally observed, which5a).areThe amounts
filled in theofmicrofracture
pyroxene and and olivine accountwith
crosscut for the
less than 10% of total primary minerals, indicating strong serpentinization
serpentine aggregates (Figure 5b). Trace amounts of chromite are also presented and included in of the parent rocks. Fine
veins of talc are locally observed, which are filled in the microfracture and crosscut with the
serpentine aggregates.
serpentine aggregates (Figure 5b). Trace amounts of chromite are also presented and included in
Results of XRD reveal that serpentine remains the most abundant mineral phase at the lower part
serpentine aggregates.
of saprolite, which
Results of is reflected
XRD by aserpentine
reveal that strong peak at 7.29
remains theÅmost
in theabundant
XRD pattern
mineral (Figure
phase 6). Thislower
at the suggests
that most of the serpentines of parent rock were retained during weathering.
part of saprolite, which is reflected by a strong peak at 7.29 Å in the XRD pattern (Figure 6). This Other components
including talc that
suggests and most
hematite areserpentines
of the also identified by XRD
of parent rockin the
weresamples
retainedfrom the lower
during part ofOther
weathering. saprolite.
Pyroxene, occurring
components as a relict
including talc andphase surrounded
hematite by the serpentine
are also identified by XRD in aggregates
the samples from(Figure
the 5c),
loweris also
part of
identified saprolite.
under Pyroxene, occurring
the microscope, but it is as a relictrare
relative phase surrounded
in the saprolite.byOlivine
the serpentine aggregates
is absolutely absent in
both (Figure 5c), is also observations
the petrographic identified underandthe microscope,
XRD patterns.but it ismay
This relative rare in
indicate thealmost
that saprolite.
all Olivine is and
of olivine
absolutely absent in both the petrographic observations and XRD patterns. This may
the majority of pyroxene were altered in the first stage of weathering. At the upper part of the saprolite, indicate that
almost all of olivine and the majority of pyroxene were altered in the first stage of weathering. At the
the mineralogical composition is not substantially changed relative to its lower analog, but there is a
upper part of the saprolite, the mineralogical composition is not substantially changed relative to its
trend of increasing in the mineral abundance of hematite and decreasing serpentine, as reflected by
lower analog, but there is a trend of increasing in the mineral abundance of hematite and decreasing
petrographic
serpentine,observations
as reflected by(Figure 5d). observations (Figure 5d).
petrographic

FigureFigure 5. Microphotographs
5. Microphotographs ofof thestudied
the studiedsamples
samples at atthe
theYuanjiang
Yuanjiang lateritic Ni Ni
lateritic profile, showing
profile, its its
showing
mineralogical composition and textures: (a) the dominant primary minerals in
mineralogical composition and textures: (a) the dominant primary minerals in the bedrock includingthe bedrock including
serpentine and pyroxene; (b) a typical mesh structure forming by serpentine, pyroxene and
serpentine and pyroxene; (b) a typical mesh structure forming by serpentine, pyroxene and magnetite;
magnetite; (c) a small amount of residual pyroxene in the serpentine dominant saprolite horizon; (d)
(c) a small amount of residual pyroxene in the serpentine dominant saprolite horizon; (d) hematite
hematite and goethite appear in the brown saprolite dominated by serpentine; (e) hematite and
and goethite appear in the brown saprolite dominated by serpentine; (e) hematite and goethite occur
goethite occur largely coexisting with a small amount of residual talc and serpentine together in the
largely coexisting
limonite with
horizon; anda small amount of
(f) concretions of hematite
residual andtalc goethite
and serpentine together
and quartz in the
grains in theuppermost
limonite horizon;
of
and (f)
the limonite horizon. Abbreviations: Go, goethite; Hem, hematite; Srp, serpentine; Qv,limonite
concretions of hematite and goethite and quartz grains in the uppermost of the horizon.
quartz; Px,
Abbreviations:
pyroxene; Tlc,Go, goethite;
talc; Hem, hematite; Srp, serpentine; Qv, quartz; Px, pyroxene; Tlc, talc;
Mag, magnetite.
Mag, magnetite.
The limonitic zone is dominated by cryptocrystalline to fine grained Fe oxides and hydroxides,
The
mostlylimonitic
goethitezone is dominated
and hematite (Figureby cryptocrystalline
5a). Goethite and hematite to finehave
grained Fe oxides
considerable and hydroxides,
overlap in XRD
patterns,
mostly goethitebutandtheyhematite
can be differentiated
(Figure 5a).byGoethite
the presence of a characteristic
and hematite peak at 4.17 Å
have considerable (goethite)
overlap in XRD
and at 2.7 Å (hematite). Under transmitted- and reflected-light, goethite appeared
patterns, but they can be differentiated by the presence of a characteristic peak at 4.17 Å (goethite) yellowish, whereas
hematite
and at retained its reddish-brown
2.7 Å (hematite). Under transmitted- color. Talc
andisreflected-light,
still well preserved (Figure
goethite 5e) in theyellowish,
appeared limonitic zone,
whereas
as shown by its characteristic peak at 9.35 Å, whereas serpentine has nearly disappeared. This
hematite retained its reddish-brown color. Talc is still well preserved (Figure 5e) in the limonitic
observation indicates that talc is present from parent rock through saprolite horizon to limonite
Minerals 2019, 9, 51 9 of 25

zone, as2019,
Minerals shown by its
9, x FOR PEER characteristic
REVIEW peak at 9.35 Å, whereas serpentine has nearly disappeared.9 This of 25
observation indicates that talc is present from parent rock through saprolite horizon to limonite horizon,
horizon, more
showing showing more
robust robust
status status thaninserpentine
than serpentine in the
the weathered weathered
products. products.
Quartz Quartz isinalso
is also presented the
presented in the upmost horizon (Figure 5f), and the unusual appearance of this
upmost horizon (Figure 5f), and the unusual appearance of this mineral may reflect an external mineral may reflect
input,
an external
because input,that
it seems because
there itare
seems that there
no rational are no
genetic rational genetic
associations associations
between quartz and between
primaryquartz and
minerals
primary minerals or those of secondary
or those of secondary weathered minerals. weathered minerals.

Figure 6.
Figure 6. X-ray diffraction
diffraction (XRD) patterns of the samples
samples from different
different horizons
horizons in the
the Ni
Ni laterite
laterite
profile. Abbreviations: Go, goethite;
profile. goethite; Hem,
Hem, hematite;
hematite;Srp,
Srp,serpentine;
serpentine;Q,
Q,quartz;
quartz;Px,
Px,pyroxene;
pyroxene;Tlc,
Tlc,talc.
talc.

5.2. Whole-Rock Geochemistry

5.2. Whole-Rock Geochemistry
The analytical results of whole-rock samples are listed in Table 1, and representative data are
The analytical results of whole-rock samples are listed in Table 1, and representative data are
graphically illustrated in Figure 7. Unweathered serpentinite is characterized by a high concentration of
graphically illustrated in Figure 7. Unweathered serpentinite is characterized by a high concentration of
Mg
Mg (38.03
(38.03wt wt% %MgO)
MgO)andandSiSi(38.8
(38.8wt
wt%%SiO
SiO2 ),2),coupled
coupledwith
withlow FeFe
low (7.49 wtwt
(7.49 %% Fe2Fe
O23O
) 3and AlAl
) and (0.8 wtwt
(0.8 %
Al O32O
% 2Al ). 3It contains
). It 0.18
contains 0.18wtwt%%Ni,
Ni,similar
similartotoultramafic
ultramaficrocks
rocksassociated
associatedwith
with lateritic
lateritic Ni
Ni deposits
deposits
elsewhere [6,15]. The saprolite samples have lower Mg (13.28–36.06 wt % MgO, mean 26.8 wt % MgO)
and higher Fe (8.44–42.27 wt % Fe2O3, mean 20.28 wt % Fe2O3) and Al (0.76–2.49 wt % Al2O3, mean
1.43 wt % Al2O3) than the unweathered serpentinite. The contents of Ni range from 0.68 to 1.18 wt %,
Minerals 2019, 9, 51 10 of 25

elsewhere [6,15]. The saprolite samples have lower Mg (13.28–36.06 wt % MgO, mean 26.8 wt % MgO)
and higher
Minerals Fe9,(8.44–42.27
2019, wt % Fe2 O3 , mean 20.28 wt % Fe2 O3 ) and Al (0.76–2.49 wt % Al2 O
x FOR PEER REVIEW , mean
103of 25
1.43 wt % Al2 O3 ) than the unweathered serpentinite. The contents of Ni range from 0.68 to 1.18 wt %,
with
with anan averageofof1.03
average 1.03wtwt%.%.Comparing
Comparing the brown brown saprolite
saprolitesamples
samplesandandthe
thepale-green
pale-greensaprolite
saprolite
samples
samples specifically,the
specifically, theformer
formerisischaracterized
characterized by a higher
higherFeFeand
andNiNiconcentrations
concentrations but a lower
but a lower MgMg
concentration than the latter. The limonitic samples exhibit a further decrease in
concentration than the latter. The limonitic samples exhibit a further decrease in Mg (mean 10.27% Mg (mean 10.27%
MgO)
MgO) andandSiSi(mean
(mean28.82%
28.82% SiO
SiO22)) relative
relativetotothe
thesaprolite samples,
saprolite butbut
samples, Fe (mean
Fe (mean44.0% Fe2OFe
44.0% 3) and Al
2 O3 ) and
mean 4.2% Al 2O3) are significantly high. The Ni content of the limonite samples is ranging from 0.47
Al mean 4.2% Al2 O3 ) are significantly high. The Ni content of the limonite samples is ranging from
wtwt
0.47 % to
%0.59 wt %,
to 0.59 wtwith an average
%, with of 0.53of
an average wt0.53
% Ni.
wtThe
% chemical differencedifference
Ni. The chemical between the red limonite
between the red
sample and brown limonite sample within the limonite horizon is mainly demonstrated by the
limonite sample and brown limonite sample within the limonite horizon is mainly demonstrated by
change of Si and Fe, and the red limonite have relatively higher Fe concentration but lower Si
the change of Si and Fe, and the red limonite have relatively higher Fe concentration but lower Si
concentration than its brown analogs. In addition, the brown limonite is geochemically characterized
concentration than its brown analogs. In addition, the brown limonite is geochemically characterized by
by hosting the highest Mn concentration in all weathered samples. The alluvium sample show a
hosting the highest Mn concentration in all weathered samples. The alluvium sample show a significant
significant high value of Si (41.05 wt % SiO2), which is consistent with the presence of quartz
high value of Si (41.05 wt % SiO2 ), which is consistent with the presence of quartz mentioned above,
mentioned above, and it also contains abundant Fe (mean 20.45 wt % Fe2O3) and Al (mean 13.2 wt %
andAlit also contains abundant Fe (mean 20.45 wt % Fe2 O3 ) and Al (mean 13.2 wt % Al2 O3 ).
2O3).

Figure
Figure 7. 7.Variations
Variationsofofthe
themajor
majorelements
elements and
and selected
selectedtrace
traceelements
elementswith
withdepth
depththrough thethe
through laterite
laterite
profile
profile with
with depth.
depth.
Minerals 2019, 9, 51 11 of 25

Table 1. Whole-rock analyses data of the samples from the Yuanjiang Ni laterite profile, including major element (wt %) and trace element (in mg/kg).

Diluvial Horizon Limonite Horizon Saprolite Horizon Bedrock

Red Limonite Brown Limonite Brown Saprolite Pale green Saprolite
P1 -19 P1 -18 P1 -16 P1 -13 P1 -11 P1 -9 P1 -7 P1 -5 P1 -2 J-3 J-1
SiO2 (wt %) 41.05 25.76 31.87 29.65 39.08 38.83 37.62 40.29 38.88 39.23 38.80
TiO2 (wt %) 0.89 0.08 0.04 0.02 0.01 0.01 0.002 0.01 0.01 0.03 0.002
Al2 O3 (wt %) 13.16 5.23 3.17 2.49 2.31 1.05 1.06 1.30 1.01 0.76 0.80
Fe2 O3 (wt %) 20.45 46.88 41.11 42.27 28.49 17.21 17.95 13.32 14.25 8.44 7.49
MnO (wt %) 0.13 0.44 1.17 0.46 0.51 0.18 0.18 0.13 0.15 0.08 0.05
MgO (wt %) 5.22 9.55 10.98 13.28 18.18 29.15 29.37 30.83 30.92 36.06 38.03
CaO (wt %) 0.04 0.02 0.04 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.05
Na2 O (wt %) 0.1 0.1 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
K2 O (wt %) 0.70 0.04 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01
P2 O5 (wt %) 0.18 0.03 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
LOI (wt %) 17.67 9.48 9.42 9.38 9.19 11.31 11.60 11.37 11.99 13.17 13.08
Cr (wt %) 0.36 0.88 0.69 0.67 0.71 0.29 0.38 0.44 0.22 0.36 0.30
Ni (wt %) 0.09 0.47 0.59 0.68 0.91 1.09 1.17 1.12 1.18 1.08 0.18
Sc (mg/kg) 34 63 65 40 33 20 17 20 15 9 8
V (mg/kg) 200 137 152 87 74 47 49 39 32 40 35
Co (mg/kg) 82 678 1493 409 391 231 242 229 185 92 100
Cu (mg/kg) 48 12 14 1 1 3 3 2 1 4 99
Zn (mg/kg) 117 199 188 122 90 54 75 57 32 46 32
Ga (mg/kg) 26 4 5 2 2 1 1 1 1 1 1
Ge (mg/kg) 3 1 2 2 1 2 2 2 1 1 1
Rb (mg/kg) 68 3 1 0.26 0.58 0.59 0.57 0.60 0.28 0.09 0.11
Sr (mg/kg) 57 4 2 1 1 1 1 1 1 1 2
Y (mg/kg) 20 3 5 26 14 4 0.31 0.30 0.15 0.11 0.11
Zr (mg/kg) 184 7 2 0.36 0.33 0.25 0.09 1 0.05 0.36 0.11
Nb (mg/kg) 18 1 0.38 0.14 0.12 0.09 0.08 0.18 0.06 0.06 0.06
Cs (mg/kg) 12 1 0.31 0.06 0.21 0.35 0.15 0.19 0.10 0.10 0.08
Ba (mg/kg) 168 15 37 60 100 31 26 19 21 5 5
Hf (mg/kg) 5 0.18 0.06 0.04 0.01 0.01 0.01 0.03 0.01 0.03 0.00
Ta (mg/kg) 1 0.06 0.03 0.01 0.01 0.02 0.01 0.06 0.00 0.01 0.01
Pb (mg/kg) 33 8 2 1 1 1 0.35 0.37 0.06 <0.01 2
Th (mg/kg) 19 1 0.23 0.01 0.02 0.02 0.02 0.07 0.00 <0.01 0.01
U (mg/kg) 4 0.22 0.07 <0.01 0.01 <0.01 <0.01 0.01 <0.01 <0.01 <0.01
Total 100.13 99.40 99.57 99.43 100.02 99.57 99.87 99.38 99.08 99.6 98.98
S/SAF 0.55 0.33 0.42 0.40 0.56 0.68 0.66 0.73 0.72 0.81 -
UMIA 42 60 51 51 35 21 22 17 18 11 10
Note: S/SAF = SiO2 /(SiO2 + Al2 O3 + Fe2 O3 ); UMIA = 100 × [Al2 O3 + Fe2 O3 ]/[SiO2 + MgO + Al2 O3 + Fe2 O3 ].
Minerals 2019, 9, 51 12 of 25

In general, the profile has a typical laterite geochemical pattern with an increase of Fe, Al, Mn and
Ti but a decrease of Si and Mg upward from the bedrock. The concentration of Ni shows a trend of
increasing in the saprolite horizon, reaching a maximum in the upper part of the saprolite horizon,
and decreasing in the limonite horizon. Cobalt has the highest value (1493 mg/kg) in the limonite
samples, and chromium shows its highest value (1.28 wt %) in the limonite sample as well. Although
the concentrations of these residual elements in weathered products are several folds higher than that
of the bedrock, none of them reached the level of economic significance.

5.3. Mineral Chemistry

Electron analysis results of selected minerals from various zones of the weathering profile
are listed in Table 2. Serpentine from fresh serpentinite contains 0.09–0.21 wt % Ni. Similar Ni
concentrations (0.16–0.21 wt %) are also observed in Talc. However, pyroxene has much lower
Ni contents (0.03–0.07 wt %), indicating that elevated Ni in the lateritic weathering profiles is unlikely
to originate from this mineral. Spinel also shows low Ni concentrations, which are mostly less than
0.1 wt % (not shown in Table 2).
Various minerals from the saprolite and limonitic zones have elevated Ni concentrations. Residual
serpentine in the saprolite has a wide range of Ni from 0.34 to 1.2 wt %, with an average of 0.87 wt %,
suggesting that the serpentine is the dominant Ni-bearing phase in the silicate ore of the Yuanjiang
lateritic Ni deposit. In addition, the residual serpentine contains lower Mg and Si but higher Fe relative
to the primary serpentine in the serpentinite, indicating that there is a chemical change during the
weathering of serpentine. Residual talc has Ni (mean 0.21 wt % Ni) comparable with values of primary
talc (mean 0.18 wt % Ni). This observation suggests that talc is not an important Ni host to the regolith,
and the residual serpentine and talc were variably enriched in Ni during lateritization.
An unidentified mineral occurring as microfracture- or open void-infillings in saprolite is also
observed (Figure 8b). This material is characterized by high Mn (14.2 wt %), Mg (17.74 wt %),
Si (15.64 wt %) and Ni (2.47 wt %), being the most Ni-enriched phase in the Yuanjiang deposit. The EMPA
results are broadly comparable to compositions of manganiferous wad (Ni-rich Mn-oxyhydroxides),
but its specific mineralogical property remains unclear and needs further investigations.
With emphasis on the mode of Ni occurrence, some selected micro-areas from a saprolite sample
were examined by elemental line scan and area scan mapping (Figure 8). Results show that Ni is
heterogeneous in the residual serpentine of different generations. The vein-like and fibrous serpentines
seem more Ni-enriched than those of flaky and tabular morphology (Figure 8a). Nickel and Mg are
negatively correlated throughout the serpentine aggregates, whereas Ni and Fe are broadly positively
correlated. Ni, Mn and Co is strongly enriched in manganiferous “wad” (Figure 8b).
Minerals 2019, 9, 51 13 of 25
Minerals 2019, 9, x FOR PEER REVIEW 13 of 25

Figure
Figure 8. Element
8. Element lines
lines andand mappings
mappings in some
in some selected
selected micro
micro areasareas
from from the silicate
the silicate ore at ore at the
the saprolite:
(a)saprolite:
elemental (a)distribution
elemental distribution in an aggregate
in an aggregate of residual
of residual serpentines
serpentines with different
with different morphology;
morphology; and (b)
and (b) elemental distribution in a manganeferous “wad” appearing in a micro area.
elemental distribution in a manganeferous “wad” appearing in a micro area.
Minerals 2019, 9, 51 14 of 25

Table 2. Electron microprobe analyses data of the primary and weathered minerals in the Yuanjiang Ni laterite profile (wt %).

Minerals in the Bedrock Minerals in the Saprolite

Primary Serpentine Weathered Serpentine Unidentified Manganiferous
Pyroxene (n = 4) Primary Talc (n = 3) Weathered Talc (n = 3)
(n = 5) (n = 16) Mineral (n = 2)
Average Range Average Range Average Range Average Range Average Range Average Range
SiO2 39.60 33.21–45.17 54.22 53.89–54.51 52.49 51.95–52.9 37.84 33.74–41.83 58.83 54.80–60.96 15.64 15.07–16.70
TiO2 0.03 0.00–0.07 0.08 0.00–0.18 0.05 0.00–0.08 0.05 0.00–0.16 0.02 0.00–0.06 0.11 0.04–0.20
Al2 O3 1.73 0.32–4.05 3.20 2.21–4.02 0.14 0.12–0.17 2.40 0.32–5.22 0.17 0.10–0.28 2.88 2.82–2.95
Fe2 O3 4.86 4.00–6.44 6.52 6.47–6.58 0.96 0.66–1.11 6.45 3.76–8.85 1.29 0.56–2.32 4.26 3.87–4.93
MnO 0.03 0.01–0.04 0.12 0.06–0.14 0.02 0.00–0.03 0.02 0.00–0.05 0.02 0.01–0.02 14.20 11.95–15.48
MgO 38.13 37.07–38.79 33.57 32.98–34.07 32.52 31.98–33.3 35.00 31.63–38.49 30.39 29.12–31.61 17.74 17.39–18.43
CaO 0.08 0.07–0.10 1.25 1.02–1.51 0.05 0.02–0.06 0.19 0.02–0.29 0.06 0.04–0.08 0.65 0.57–0.81
Na2 O 0.00 0.00–0.00 0.02 0.00–0.04 0.04 0.01–0.07 0.02 0.00–0.03 0.01 0.00–0.02 0.44 0.09–1.14
K2 O 0.01 0.00–0.02 0.01 0.00–0.02 0.04 0.03–0.05 0.02 0.00–0.06 0.01 0.00–0.02 0.04 0.02–0.06
Cr 0.21 0.00–0.49 0.44 0.4–0.46 0.12 0.05–0.2 0.74 0.12–1.57 0.1 0.1–0.1 0.06 0.02–0.12
Ni 0.16 0.09–0.21 0.05 0.03–0.07 0.18 0.16–0.21 0.87 0.34–1.20 0.21 0.18–0.26 2.47 2.15–2.92
Co 0.00 0.00–0.00 0.00 0.00–0.00 0.00 0.00–0.00 0.00 0.00–0.00 0.01 0.01–0.02 1.84 1.78–1.94
Minerals 2019,9,9,51
Minerals2019, x FOR PEER REVIEW 1715ofof2525

6.6.Discussions
Discussions
6.1. Lateritization History
6.1. Lateritization History
The chemical index of alteration (CIA, CIA = [Al2 O3 /(Al2 O3 + CaO* + Na2 O + K2 O)]
×100 The (%)) chemical index used
[43] is a widely of alteration
indicator (CIA, CIA = [Al2the
for estimating O3/(Al 2O3 +of
degree CaO* + Na2O of
weathering +K 2O)] ×100
rocks. This (%)) [43]
indicator,
is a widely
however, used
is not indicator
effective for estimating
enough to revealthe thedegree of weathering
weathering degree ofofour rocks. Thisultramafic
studied indicator, however,
rock since
is not
the rockeffective
of this typeenough to reveal
commonly the weathering
contains degree of our
low concentrations studied
of CaO, Naultramafic rock since the rock
2 O and K2 O. Thus, concerning
of this type commonly contains low concentrations of CaO, Na
the weathering of mafic or ultramafic rocks specifically, the S/SAF value (S/SAF concerning
2O and K 2 O. Thus, = SiO2 /(SiO the
2 +
weathering of mafic or ultramafic rocks specifically, the S/SAF value (S/SAF
Al2 O3 + Fe2 O3 ) [44], or the UMIA value (the ultramafic index of alteration, UMIA = 100 × [(Al2 O3 = SiO 2/(SiO2 + Al2O3 +

+FeFe2O 3) [44], or the UMIA value (the ultramafic index of alteration, UMIA = 100 × [(Al2O3 + Fe2O3)/(SiO2
2 O3 )/(SiO2 + MgO + Al2 O3 + Fe2 O3 )] [20] might be better choices for the weathering degree
+ MgO
evaluation, + Albecause
2O3 + Fe2O3)] [20] might be better choices for the weathering degree evaluation, because
MgO and SiO2 tend to be leached out but Al2 O3 and Fe2 O3 are commonly
MgO and SiO 2 tend to be leached out but Al2O3 and Fe2O3 are commonly enriched in the lateritic
enriched in the lateritic profiles. Applying the S/SAF index, we found that the regolith samples
ofprofiles.
Yuanjiang Applying
profilethe S/SAF
have an index,
S/SAFwe found
value of that the regolith
0.33–0.8. samples
It is higher than of other
Yuanjiang profile reported
previously have an
S/SAF value of 0.33–0.8. It is higher than other previously reported
cases in modern rainforest condition. For instance, the Kolonodale lateritic Ni profile on Sulawesi cases in modern rainforest
condition.
Island, For instance,
Indonesia, shows an theS/SAF
Kolonodale
value lateritic
ranging Ni profile[15].
0.04–0.66 on Sulawesi
In addition,Island, Indonesia,
in the SiO2 –Al2shows
O3 –Fe2anO3
S/SAF value ranging 0.04–0.66 [15]. In addition, in the SiO2–Al2O3–Fe2O3 ternary diagram (Figure 9),
ternary diagram (Figure 9), the samples are plotted in the weak to moderate lateritization domain.
the samples are plotted in the weak to moderate lateritization domain. Applying the UMIA index,
Applying the UMIA index, the saprolite samples of this study have UMIA values in the range of
the saprolite samples of this study have UMIA values in the range of 17–51 and limonite samples
17–51 and limonite samples reach UMIA values up to 60, which is lower than those examples of
reach UMIA values up to 60, which is lower than those examples of strong weathered condition with
strong weathered condition with UMIA values beyond 90, such as in Cuba and the Dominican
UMIA values beyond 90, such as in Cuba and the Dominican Republic [20] Hence, both the S/SAF
Republic [20] Hence, both the S/SAF and UMIA index indicate that the Yuanjiang lateritic Ni profile
and UMIA index indicate that the Yuanjiang lateritic Ni profile has experienced a not very strong
has experienced a not very strong lateritization process. This result is also corroborated by the
lateritization process. This result is also corroborated by the geological and mineralogical
geological and mineralogical characteristics of the profile. Specifically, the limonite horizon, which
characteristics of the profile. Specifically, the limonite horizon, which is an indication of strong
is an indication of strong lateritization process, is only developed with a thin thickness. Meanwhile,
lateritization process, is only developed with a thin thickness. Meanwhile, the Fe-oxyhydroxides,
the Fe-oxyhydroxides, which reflect a mineral indicator of the strong lateritization process, are less
which reflect a mineral indicator of the strong lateritization process, are less abundant in the mineral
abundant in the mineral compositions of the regolith samples. Thus, according to the above evidence,
compositions of the regolith samples. Thus, according to the above evidence, we speculate that the
we speculate that the Yuanjiang profile is a product of weak to moderate level lateritization process.
Yuanjiang profile is a product of weak to moderate level lateritization process. This relatively less
This relatively less intense lateritization degree of regolith may provide a possible explanation of
intense lateritization degree of regolith may provide a possible explanation of why no garnierite ore
why
wasno garnierite
observed ore was observed
in Yuanjiang deposit, in Yuanjiang
which deposit,
is usually which is
considered asusually
a product considered
of strongas a product
infiltration
ofprocess
strongunder infiltration
highly lateritization condition [15,24,45,46]. This situation of Yuanjiang deposit isof
process under highly lateritization condition [15,24,45,46]. This situation
Yuanjiang deposit
similar to the Riddle is similar
depositto the
in Riddle
Oregon,deposit in Oregon,
USA, where thereUSA,
is no where there isgarnierite-type
significant no significant
garnierite-type
mineralization mineralization within the
within the Ni-bearing Ni-bearing
silicate zone silicate zone either.
either. Foose Foose [39]that
[39] addressed addressed
it might that
beit
might be attributed to the relatively short
attributed to the relatively short weathering history. weathering history.

Figure9.9.Lateritization
Figure Lateritization degree
degree of the Yuangjiang lateritic
lateritic Ni
Ni profile
profile and
and its
its relationship
relationshipto
toelement
element
concentrationsof
concentrations ofdifferent
differentsamples.
samples.

ItItisiswell
well accepted
accepted thatthat thelaterite
the Ni Ni laterite is principally
is principally regulated regulated by climatic
by climatic condition.condition. Most
Most Cenozoic
Cenozoic
lateritic Nilateritic
depositNiare
deposit
mainly aredistributed
mainly distributed in a restricted
in a restricted latitudelatitude
range of 22◦ of
range N 22° N ◦toS,22°
to 22 S, a
a zone
zone dominated
dominated by tropical
by tropical to subtropical
to subtropical climate
climate [5].[5]. It is
It is furtherestablished
further established that
that the lateritic
lateritic Ni
Ni
mineralizationisisparticularly
mineralization particularly favored
favored by warmwarm (mean annual annual temperature
temperature of of 19-29
19–29°C)◦ C)and
andhumid
humid
(yearlyprecipitation
(yearly precipitationofof1000–3200
1000-3200 mm)mm) conditions [14]. Currently,
Currently, the
the Yuanjiang
Yuanjiang district
districtisislocated
locatedatat
◦
22.5° N latitude,
22.5 N latitude, with an average annual temperature of 21 °C ◦ and an average yearly
average annual temperature of 21 C and an average yearly precipitation precipitation of
of1100
1100 mm. mm. Such a climatic
Such condition
a climatic is justisatjust
condition theatmargin of the “climate
the margin window”
of the “climate favoringfavoring
window” the lateritic
the
Minerals 2019, 9, 51 16 of 25

lateritic weathering and associated Ni mineralization. Hence, the Ni laterite in Yuanjiang area is not
the product of present climate environment alone but producer of its entire weathering history.
To answer when the lateritization began and how long it has lasted in Yuanjiang area is still a
big challenge, since there is no reliable isotopic approach to constrain the history of the weathering of
the ultramafic rocks. Previous work has depended on geological evidence to trace the lateritization
history and understand the related climatic background. For example, there are many fossil lateritic Ni
deposits along the Tethyan ophiolite belts, such as the Çaldag deposit in Turkey [11], Bitincke deposit
in Albania [13] and those in Greece [47] and Oman [16], which are underlain sediments of known
age. The stratigraphic relations thus provide indirect, minimum age constraints on lateralization and
paleoclimatic conditions under which the lateritic Ni deposits formed. However, such stratigraphic
correlations are lacking at Yuanjiang, and their formation ages remain undetermined. Thus, the climatic
background and evolutional history responsible for the formation of the Yuanjiang lateritic Ni deposit
can only be inferred from some regional paleoclimatic proxies. The complete history of the Yuanjiang
deposit can be traced to the late Triassic, when the ophiolites (the parent rock of the Yuanjiang deposit)
were tectonically emplaced [30,31]. Unfortunately, the available paleoclimatic materials involving
in the study site and regional areas are limited to a period from early Jurassic to present. Even so,
the existing paleoclimatic materials from previous works may shed light to understand this issue.
Previous paleoclimatic studies show that, from the early Jurassic to late Cretaceous, the study
area was characterized by arid to semi-arid subtropical climate with limited precipitation [48,49].
The aridity is well reflected by the widespread red beds containing abundant gypsum, halite, potash
salt, mirabilite, and glauberite in many Jura-Cretaceous terrestrial basins in southwestern and southern
China [49]. During this period, the climate condition was unconducive to the lateritization of ultramafic
rocks. In late Oligocene, warm and humid climate emerged in south China, including the study area,
as indicated by the presence of coal beds around the Oligocene-Miocene boundary in many terrestrial
basins over the Yunnan Plateau [34]. Abundance of thick lignite deposits and oil shales in several
Miocene to Pleistocene basins over the Yunnan Plateau confirms the prevalence of humid climates
during the whole Neogene [34,50,51]. Well preserved fossil tropical–subtropical flora and fauna
contained in some Miocene to Pliocene sediments provide additional evidence for humid climatic
conditions [52–54]. Recent studies propose that the emergence of warm and humid climate in the
Oligocene-Miocene boundary in the Yunnan Plateau has been genetically linked to the establishment
of the Indian summer monsoon, which likely was due to significant uplift of the Tibet plateau at the
same time [36,55–58]. The Indian summer monsoon must have brought abundant precipitation in
SW China, which resulted in intense weathering and formation of the lateritic regolith. Supportive
evidence includes the emergence of abundant supergene Mn deposits aged from 9.3 to 0.16 Ma in south
China, particularly in Yunnan Province and adjacent Guangxi Province [36,59]. The formation of these
supergene Mn deposits closely coincided with the intensification of the Indian summer monsoon [36],
suggesting a causal link between lateritic weathering and the monsoonal climate. Thus, by inference,
we speculate that the formation of the Yuanjiang lateritic Ni deposit might have a similar weathering
timing and climatic background with those Neogene supergene Mn deposits. The humid climate
conducive to lateritization of ultramafic rocks and supergene Ni enrichment in Yuanjiang area has
probably prevailed since at least the late Miocene until the present. However, further geochronological
work will hopefully provide precise age constraints on the lateritic Ni mineralization.

6.2. Impact of Tectonic Uplift

Large areas of the whole Yunnan Plateau are characterized by repeated uplift since the
Pliocene [60,61], as indicated by the staged river incision and the stepped topography over this
plateau. In the study area, the stepped topography is best illustrated by six-level denudation planes
between 1700 and 2100 m on both sides of the Anding River. This suggests that the tectonic uplift in
the Yuanjiang area and exerted a significant role in shaping the local geology and landscape.
Minerals 2019, 9, 51 17 of 25

The impact of tectonic uplift on weathering can be discerned from the occurrence of regolith
profile. We notice that a thick saprolite horizon is stably developed within the serpentinite-derived
regolith in study area, and it is usually thought to be controlled by the drainage condition in local
hydrology [62]. Given the coupling of weathering and uplift time, uplift can enhance the relief, lower
the water table and ultimately lead to the weathering front moving downward to deeper [3,21].
In addition, this tectonic-induced topographic change is considered to be conductive for enhancing
recharge, infiltration, and reaction of groundwater [25]. It is probably the main reason a thick saprolite
is the dominant unit of the regolith in study area. Conversely, tectonic uplift has also exerted a
negative influence on regolith formation. It is thought to have promoted erosion, river incision,
and subsequently result in the segmentation and thinning of the lateritic regolith [36]. The uplift-
and river incision-induced erosion may explain a number of phenomena regarding to the field
occurrence of regolith in Yuanjiang area, including the absence of lateritic Ni regolith at the highest
elevations (VI-level planation surface), the isolation of weathering regolith on the stepped III-level and
IV-level denudation planes, and the presence of only thin limonite horizon at the upper part of the
regolith profile.

6.3. Mechanism of Ni Mineralization

To answer why Ni is enriched within the serpentinite-derived regolith in Yuanjiang area and
explain the detailed mineralization features of this deposit, it is necessary to assess elemental behavior
during lateralization. Numerous authors have mathematically used mass-balance calculations to
estimate losses or gains of elements with the rock weathering, and various methods of the mass-balance
calculation have been proposed. One possible choice is the chemical compositions based method [63–68],
in which an immobile element selection is needed for normalization of compositions of the lateritic
profiles [15,69,70]. However, in practical applications, discussion of which elements to use for mass
balance calculations is commonly difficult. The other possible choice is the chemical compositions and
physical properties integrative based method, in which the mass-balance calculation is expressed as a
function of the constitutive relationships between the chemical compositions of parent and weathered
material, their bulk densities, and volumes [42,71,72]. In this study, the parental rock structures are
well preserved in the saprolite, which suggests that weathering processes have preserved the original
volume [42]. Based on the assumption that the volume has not greatly varied between bedrock
and saprolite, as well as the saprolite is the dominant unit of the profile, the volume mass-balance
calculations can be applied. The net gains and losses of chemical constituents are calculated using the
following equation [73]: " ! #
Cjw × ρ jw
Kj = − 1 × 100
Cjp × ρ jp

where Kj is the gain and/or loss factor of chemical element j; Cjw and Cjp are the concentrations of
chemical element j in the weathered layer, w, and the parent material, p, respectively; and ρjw and ρjp
are bulk densities of the weathered material, w, and the parent material, p, respectively.
As illustrated in Figure 10, many major elements (e.g., Mg, Si, Ca, Na and Cr) display an absolute
loss throughout the profile. These elements tend to be most significantly depleted towards the upper
zone of the lateritic profile (limonitic zone), with samples at base of the saprolite being least depleted.
Over 60% of MgO (Kj = −60) in the saprolite horizon, and even 89% of them were removed (Kj = −89) in
the limonite horizon. Silica is largely lost, with nearly 70% (Kj = −70) in the limonite and nearly 36–63%
(Kj = −36~−63) in the saprolite. Manganese concentration increases throughout the profile, notably in
the lower part of the limonite and the upper part of the saprolite (Figure 10). This observation indicates
that external Mn may have been introduced into the weathering profile by lateral flow of weathering
solutions. The externally derived Mn may precipitate in joints and fractures of the weathered products
as partly confirmed by the presence of manganiferous wad.
Minerals 2019, 9, 51 18 of 25

Nickel displays a slight loss in the red limonite (Kj = −10), but begins to exhibits a marked gain in
the brown limonite (Kj = +45) and more significantly in the saprolite (Kj = +84~+316). This observation
is consistent with several previous studied cases [15], and it can be explained by a well-accepted
view that Ni is leached from in the upper of the profile and subsequently adsorbed in the lower part.
The mobility of Ni, however, is complex and it may have various associations with the evolution of
minerals, organic matter, pH environment and other factors during the lateralization. Nickel originated
from the primary serpentine, which contains 0.09–0.21 wt % Ni. Pyroxene (0.03–0.07 wt % Ni) may
have made a lesser contribution since they only account for a small proportion of the whole primary
minerals. With the decomposition of these primary minerals, some Ni may have been leached in the
first phase of weathering of serpentine and likely transported downward as bicarbonate or complexed
with organic matters in weathering solutions [73–75].
After released from ultramafic parent rock to weathering solution, the mobility of Ni is to a great
extent controlled by sorption, substitution and dissolution/precipitation processes, and the leached
Ni can be fixed in various supergene minerals at different depths of a weathering profile [27,76–78].
In detail, at least three types of minerals were identified as the Ni-rich carriers and being responsible for
the adsorption of Ni in the Yuanjiang profile. Firstly, in the upper part of the Yuanjiang lateritic profile,
Ni was thought to be fixed in goethite due to its large surface area and open channel structure [79].
This view was confirmed by the XRF analytical results of the whole-rock samples in the limonitic
zone, which is dominated by the goethite and hematite and have 0.6–1.2% Ni. Secondly, our EMPA
analysis found a Ni-bearing manganiferous phase in the brown limonite sample with Ni concentrations
up to 3.14 wt %, which suggest that Ni may be fixed to the manganiferous phase in some specific
locations. However, this occurrence of Ni enrichment is relatively less as a whole. Notably, Ni could
be expelled from goethite as it ages through successive dissolution and recrystallization cycles during
the lateritization process [78], which promoted Ni migration downward to the lower part of regolith
profile. In this position, part of the leached Ni may be fixed by silicate minerals based on the fact of
high Ni concentration (0.34–1.2 wt % Ni) in the weathered serpentine. The Ni2+ in weathering solutions
tend to substitute for Mg2+ in the structure of serpentine due to their similar ionic radius, particularly
under alkaline conditions [64,76]. By means of Ni K-edge µEXAFS, it was confirmed that Ni was
found in Ni–Mg and Ni–Ni mixed sites in Ni-bearing secondary serpentines [22]. Based on above
observations and relevant knowledge, it is thus proposed that Ni mineralization in the Yuanjiang
profile was mainly related to ion exchange reactions between the serpentine and weathering solution.
In contrast, talc is not an active mineral for Ni ion exchange reaction in the saprolite horizon despite
it is largely retained during the saprolitization. This view is supported by the low Ni concentration
(0.18–0.26 wt % Ni) in the weathered talc of the silicate ore.
Besides Ni, Co is also worthy of attention for its potential economic significance in the laterite
profile derived from the ultramafic rocks. Some lateritic Ni deposits contain significant amounts of Co
that can be produced as a by-product. Examples include the Goro deposit in New Caledonia [10,80],
Çalda deposit in Turkey [11] and Wingellina deposit in Australia [17]. At Yuanjiang, Co has a similar
mobility behavior with Mn, as illustrated in Figure 10, owing to their geochemical affinity during the
lateritization process [81–83]. Cobalt commonly preferentially enters the structure of low-crystallinity
Mn-oxyhydroxydes by substitution in the lower part of the limonite horizon [8,12,17,84]. However,
although some Co-bearing manganiferous “wad” (2 wt % Co) was occasionally identified in the studied
elsewhere profile, whole-rock Co concentration maximum is only 0.15%, much lower than many Ni
lateritic profiles such as Nkamouna profile in Cameroon (up to 0.84 wt % Co) [83] and Bulong profile in
Australia (up to 2 wt % Co) [85]. The explanation of why Co mineralization is lacking in the Yuanjiang
profile, firstly, may lie in the lower Co concentrations in the parent rocks, and, secondly, may be
associated with the rare occurrence of Mn-oxyhydroxydes in the regolith, because Mn precipitation in
regolith generally depends on late-stage mobility related to local drainage, geomorphology and other
environmental conditions.
Minerals 2019, 9, 51 19 of 25
Minerals 2019, 9, x FOR PEER REVIEW 21 of 25

Figure
Figure 10.10. Results
Results of the
of the geochemical
geochemical mass-balance
mass-balance calculations
calculations of some
of some representative
representative elements
elements along
thealong the profile.
profile.

6.4.6.4.
Genetic Model
Genetic Modelforforthe
theYuanjiang
YuanjiangLateritic
LateriticNi
Ni Deposit
Deposit
Large
Largeaccumulation
accumulationofofsupergene
supergene Ni-rich
Ni-rich minerals results from
minerals results fromthe theinteractions
interactionsofofoxidized
oxidized
meteoric waters with Ni-bearing
meteoric waters with Ni-bearing precursor precursor rocks under an optimum combination
under an optimum combination of lithological, of lithological,
climatic,
climatic, and and structural
structural factors
factors [4,5,7,21].These
[4,5,7,21]. Thesefactors
factorscontribute
contributeto tothe
theformation
formation and and preservation
preservation of
theofregolith
the regolith
in the inregion
the region
andand to the
to the development
development of the
of the Yuanjiang
Yuanjiang NiNi laterite
laterite deposit.
deposit.
TheThe Ni-bearingprecursor
Ni-bearing precursorrocksrocksof ofYuanjiang
Yuanjiang Ni deposit
depositisislinked
linkedtotothe theAilaoshan
Ailaoshan paleo-Tethyan
paleo-Tethyan
ophiolites (Figure 11a). They are considered to be derived from the
ophiolites (Figure 11a). They are considered to be derived from the break-up of the Ailaoshan break-up of the Ailaoshan ocean
ocean
basin
basin ininthe
theearly
early Carboniferous
Carboniferous[32]. [32].With
Withthethe
subduction
subduction and andclosure of the of
closure Ailaoshan ocean basin
the Ailaoshan ocean
in late
basin in Triassic, fragments
late Triassic, of the ophiolites
fragments were tectonically
of the ophiolites emplaced into
were tectonically the middle
emplaced intotothe
latemiddle
Triassic to
forming a mélange along the Ailaoshan orogenic belt [30,31]. From the
late Triassic forming a mélange along the Ailaoshan orogenic belt [30,31]. From the late Triassic late Triassic to Cretaceous, the to
ophiolite remnants were greatly impacted by the lndosinan-Yanshanian orogenic thrust, and the
Cretaceous, the ophiolite remnants were greatly impacted by the lndosinan-Yanshanian orogenic
ultramafic rocks within the ophiolite belt experienced multiple stages of deformation and
thrust, and the ultramafic rocks within the ophiolite belt experienced multiple stages of deformation
metamorphism [32]. Large numbers of ultramafic bodies were compressed, fragmentized and even
and metamorphism [32]. Large numbers of ultramafic bodies were compressed, fragmentized and even
altered by syntectonic hydrothermal fluids [32]. The widely observed talc-veins filled in the
altered by syntectonic hydrothermal fluids [32]. The widely observed talc-veins filled in the serpentinite
serpentinite bodies in Yuanjiang area are speculated to have been formed at this time. Meanwhile,
bodies in Yuanjiang area are speculated to have been formed at this time. Meanwhile, the ophiolite
the ophiolite remnants probably outcropped at the surface at this orogenic time. Onset of the regional
remnants probably outcropped
intense weathering of outcropped at the surface
rocks may athave thisstarted
orogenic in thetime.
lateOnset of the[34,36,51,59].
Oligocene regional intense
As
weathering of outcropped rocks may have started in the late Oligocene
discussed, the emergence of humid and warm climates linked to Indian monsoon resulted in the [34,36,51,59]. As discussed,
theweathering
emergenceofof exposedhumid and warm
rocks, andclimates linked formed
subsequently to Indian themonsoon resulted
thick lateritic in the overlying
regolith weathering
of ultramafic
exposed rocks, rocks in Yuanjiang area. Given the coupling of regional weathering and uplift timerocks
and subsequently formed the thick lateritic regolith overlying ultramafic [36], in
Yuanjiang
the upliftarea. Given the
contributed coupling
to the of regional
deepening weathering
of the regolith and uplift
by impacting time
local [36], theon
hydrology uplift
one contributed
the hand,
to while
the deepening
its periodic of activity
the regolith by the
caused impacting
isolationlocal hydrology
of regolith and on onethem
raised the hand, while its
to different periodic
altitudes,
activity
formingcaused the isolation
the stepped of regolith
distribution pattern,and
on raised
the otherthem to different altitudes, forming the stepped
hand.
The development
distribution pattern, on the of the Ni,hand.
other mineralized regolith can be regarded as an advancement history of
a weathering
The development front moving
of the Ni,from the surface
mineralized to below
regolith can bethe water as
regarded table [21], coupled history
an advancement with Ni of a
redistribution from the primary minerals of bedrock to the weathered
weathering front moving from the surface to below the water table [21], coupled with Ni redistribution minerals within regolith
(Figure
from 11b). Lateral
the primary infiltration
minerals of water
of bedrock richweathered
to the in dissolvedminerals
Ni couldwithin
also contribute
regolith to local enrichment
(Figure 11b). Lateral
of Ni down slope topography [26]. Weathering was preferentially
infiltration of water rich in dissolved Ni could also contribute to local enrichment of Ni downdeveloped in areas where joints
slope
and faults are most developed. The structurally enhanced permeability
topography [26]. Weathering was preferentially developed in areas where joints and faults are most significantly promoted
oxidation of bedrock to form a ferruginous cover dominated by Fe-oxyhydroxydes at the surface of
developed. The structurally enhanced permeability significantly promoted oxidation of bedrock to
Minerals 2019, 9, 51 20 of 25

form a ferruginous
Minerals 2019, 9, x FORcover
PEER dominated
REVIEW by Fe-oxyhydroxydes at the surface of the ultramafic rocks 22 of[7,15],
25
characterized by an increase in Fe and Al and a strong decrease in Mg, Si and Ca. Some Ni2+ released
from
thethe primary
ultramafic minerals
rocks [7,15],ischaracterized
adsorbed byby goethite at the
an increase in limonite
Fe and Alhorizon, as atdecrease
and a strong the Çalda inğMg,
deposit
Si
in and Ca. Some
Turkey [13]. Ni 2+ released from the primary minerals is adsorbed by goethite at the limonite horizon,
Thus, the oxide ore (I-type) was formed firstly. As the weathering front moved
to as at the Çaldağ
a deeper deposit inmay
level, oxidation Turkey
have[13]. Thus,influence
a weak the oxideonore the(I-type) was formed
lateritization, firstly.
but the As the
groundwater
weathering front moved to a deeper level, oxidation may have a weak influence
activities and rock–water interaction may play a more important role below the water table. Particularly,on the lateritization,
but the groundwater
ion-exchange activities the
process between andphyllosilicate
rock–water interaction
mineralsmay andplay a more
leached important solution
weathering role below maythe be
water table. Particularly, ion-exchange process between the phyllosilicate minerals
prevailing [86]. Theoretically, the leached Ni in solution may tend to substitute for Mg in the structure and leached
of weathering
serpentine at solution
alkaline may be prevailing
conditions [21]. [86]. Theoretically,
Therefore, the leachedof
the accumulation NiNi-rich
in solution may
silicate tend to at
minerals
substitute for Mg in the structure of serpentine at alkaline conditions [21]. Therefore, the
the saprolite horizon produced the silicate Ni ore (III-type), similar to the reports from Kolonodale
accumulation of Ni-rich silicate minerals at the saprolite horizon produced the silicate Ni ore (III-
deposit in Indonesia [15]. Regarding the oxide and silicate mixed ore (II-type), it represents the
type), similar to the reports from Kolonodale deposit in Indonesia [15]. Regarding the oxide and
mineralogical and chemical transition between types I and III, and genetically it may be formed at a
silicate mixed ore (II-type), it represents the mineralogical and chemical transition between types I and
specific hydrological regime of water table fluctuations.
III, and genetically it may be formed at a specific hydrological regime of water table fluctuations.
In summary, the Yuanjiang lateritic Ni deposit may have formed by the following scenarios: (1)
In summary, the Yuanjiang lateritic Ni deposit may have formed by the following scenarios: (1)
development
development ofofAilaoshan
Ailaoshanpaleo-Tethyan
paleo-Tethyan ophiolites in early
ophiolites in earlyCarboniferous;
Carboniferous;(2)(2)tectonic
tectonic emplacement,
emplacement,
deformation,
deformation,metamorphism
metamorphismand and exposure
exposure of of the
the ophiolites
ophiolitesremnants
remnantsininlatelate Triassic
Triassic to to Cretaceous;
Cretaceous;
(3)(3)
weathering of ophiolites remnants and supergene Ni enrichment starting at
weathering of ophiolites remnants and supergene Ni enrichment starting at least in late Oligoceneleast in late Oligocene
under a humid subtropical climate; and (4) multi-stage lifting by syn-weathering
under a humid subtropical climate; and (4) multi-stage lifting by syn-weathering period uplift and period uplift and
consequently
consequently segmentation
segmentationofofNi Nilaterite.
laterite.

Figure
Figure 11.11.Formation
Formation and and evolution
evolutionhistory
historyof of
thethe
Yuanjiang
Yuanjianglateritic Ni deposit.
lateritic (a) A regional
Ni deposit. scale
(a) A regional
interpretation. C-T : Development of the Ailaoshan paleo-Tethyan ophiolites;
scale interpretation. C-T2 : Development of the Ailaoshan paleo-Tethyan ophiolites; T3 -K: Tectonic
2 T3 -K: Tectonic
emplacementand
emplacement andexposure
exposureofofthe theophiolites
ophiolites remnants;
remnants; N-Q:
N-Q:Weathering
Weatheringofofthe theophiolites
ophiolites remnants
remnants
and formation of Ni laterite at the stepped landscape. (b) A profile scale interpretation.
and formation of Ni laterite at the stepped landscape. (b) A profile scale interpretation. I: Oxidation of I: Oxidation
theofbedrock
the bedrockandand formation
formation of the
of the ferruginouscover.
ferruginous cover.II:
II:Differentiation
Differentiation of ofthe
thelimonite
limoniteand andsaprolite
saprolite
with weathering front moved downward. Starting appearance of the oxide ore
with weathering front moved downward. Starting appearance of the oxide ore and mixed oxide-silicate and mixed oxide-
silicate ore. III: Deepening of each regolith unit impacted by tectonic uplifting and erosion of the upper
ore. III: Deepening of each regolith unit impacted by tectonic uplifting and erosion of the upper part of
part of the Ni laterite. The silicate ore was significantly formed at this stage.
the Ni laterite. The silicate ore was significantly formed at this stage.

7. Conclusions
7. Conclusions
TheThe Yuanjiang
Yuanjiang lateritic
lateritic NiNi depositcan
deposit canbebeclassified
classifiedasasaasilicate
silicatesubtype
subtypewith
with phyllosilicates
phyllosilicates and to
to a lower extent Fe-oxides as the main Ni-hosting phases. Compared
a lower extent Fe-oxides as the main Ni-hosting phases. Compared to similar examples to similar examples worldwide,
worldwide,
it possesses
it possesses similarities
similarities in profile
in profile geologygeology and Ni-hosting
and Ni-hosting minerals, minerals, but presents
but presents significant
significant differences
differences in ore types, especially lacking of the high grade garnierite ore. Three types of
in ore types, especially lacking of the high grade garnierite ore. Three types of lateritic Ni ores (oxide lateritic Ni
ores (oxide ore, oxide-silicate mixed ore and silicate ore) are identified throughout the
ore, oxide-silicate mixed ore and silicate ore) are identified throughout the regolith profile, and it regolith profile,
and itthe
reflects reflects the complex
complex Ni redistribution
Ni redistribution history history with serpentinite
with serpentinite lateritization
lateritization controlled
controlled by bothbymineral
both
mineral composition of parent rock and weathering environment. Ni is preferentially enriched in
composition of parent rock and weathering environment. Ni is preferentially enriched in serpentine
serpentine (0.34–1.2 wt % Ni) rather than talc (0.18–0.26 wt % Ni) despite their similarity in
(0.34–1.2 wt % Ni) rather than talc (0.18–0.26 wt % Ni) despite their similarity in mineralogical nature.
mineralogical nature.
Geochemical index (S/SAF and UMIA values) indicate that the studied serpentinite-derived
Geochemical index (S/SAF and UMIA values) indicate that the studied serpentinite-derived Ni-
Ni-rich regolith has experienced, at least, weak to moderate level lateritization that probably emerged at
rich regolith has experienced, at least, weak to moderate level lateritization that probably emerged at
the Oligocene-Miocene and continued to the present. Recent weathering is probably not lateritization,
Minerals 2019, 9, 51 21 of 25

the Oligocene-Miocene and continued to the present. Recent weathering is probably not lateritization,
but is modifying the pre-existing lateritic regolith. The formation of the Yuanjiang lateritic Ni deposit
is closely linked to regional multi-staged tectonic uplift during the development of Yunnan Plateau.
This active tectonic setting has promoted weathering of serpentinite and supergene Ni enrichment,
but is also responsible for its partial erosion.

Author Contributions: All authors contributed in a substantial way to the manuscript. W.F. conceived and
designed the work that led to the submission, acquired data, and played an important role in interpreting the
results. Y.F. contributed significantly to analysis and manuscript preparation. P.L. performed to analyse the data.
Y.Z performed the experiments. X.H. revised the manuscript. X.Z. contributed to field sampling work. Q.C.
designed the experiments. Y.Z. helped perform the analysis with constructive discussions.
Acknowledgments: This research was financially supported by the National Natural Science Foundation
(41462005) and the project of Collaborative Innovation Center for Exploration of Hidden Nonferrous Metal
Deposits and Development of New Materials in Guangxi. We acknowledge the support of the Yuanjiang Nickel
Mining Co., Ltd. for our field investigation. The authors also express gratitude to Hongyi Chen for his assistance
with microprobe analysis at the Guilin University of Technology, and Jianlin Chen for his aid with bulk geochemical
analysis at the Key Laboratory of Geochronology and Geochemistry, Chinese Academy of Sciences. This paper
has also benefited greatly from comments and suggestions by Jianwei Li of China University of Geosciences. We
appreciate careful and exhaustive comments and revisions of two anonymous journal reviewers, which improved
the manuscript.
Conflicts of Interest: The authors declare no conflict of interests.

References
1. Dalvi, A.D.; Bacon, W.G.; Osborne, R.C. Past and future of nickel lateritic projects. International laterite Nickel
Symposium, Perth, Australia, 28 September–1 October 2004; Charlotte, N.C., Imrie, W.P., Lane, D.M., Eds.; TMS:
Warrendale, PA, USA, 2004; pp. 23–50.
2. Berger, V.I.; Singer, D.A.; Bliss, J.D.; Moring, B.C. Ni-Co Lateritic Deposits of the World—Database and Grade and
Tonnage Models; Open-File Report; U.S. Department of the Interior & U.S. Geological Survey: Reston, VA,
USA, 2011; Volume 1058, pp. 1–26.
3. Butt, C.R.M.; Cluzel, D. Lateritic Nickel ore deposits: Weathered serpentinites. Elements 2013, 9, 123–128.
[CrossRef]
4. Brand, N.W.; Butt, C.R.M.; Elias, M. Nickel lateritic: Classifications and features. AGSO J. Aust. Geol. Geophys.
1998, 17, 81–88.
5. Elias, M. Nickel Lateritic Deposits-Geological Overview, Resources and Exploitation, in Giant Ore Deposit:
Characteristics, Genesis and Exploration; Special Publication; Centre for Ore Deposit Research, University of
Tasmania: Tasmania, Australia, 2002; Volume 4, pp. 205–220.
6. Gleeson, S.A.; Herrington, R.J.; Durango, J.; Velázquez, C.A. The mineralogy and geochemistry of the Cerro
Matoso S.A. Ni lateritic deposit, Montelíbano, Colombia. Econ. Geol. 2004, 99, 1197–1213. [CrossRef]
7. Freyssinet, P.; Butt, C.R.M.; Morris, R.C. Ore-forming processes related to lateritic weathering. Econ. Geol.
2005, 681–722.
8. Fouateu, R.Y.; Ghogomua, R.T.; Penaye, J.; Ekodecka, G.E.; Stendalc, H.; Colin, F. Nickel and cobalt
distribution in the lateritics of the Lomié region, south-east Cameroon. J. Afr. Earth Sci. 2006, 45, 33–47.
[CrossRef]
9. Lewis, J.F.; Draper, G.; Proenza, J.A.; Espaillat, J.; Jimenez, J. Ophiolite-Related Ultramafic Rocks
(Serpentinites) in the Caribbean Region: A Review of their Occurrence, Composition, Origin, Emplacement
and Ni-Lateritic Soils Formation. Geol. Acta 2006, 4, 237–263.
10. Wells, M.A.; Ramanaidou, E.R.; Verrall, M.; Tessarolo, C. Mineralogy and crystal chemistry of “garnierites”
in the Goro lateritic nickel deposit, New Caledonia. Eur. J. Miner. 2009, 21, 467–483. [CrossRef]
11. Thorne, R.L.; Herrington, R.; Roberts, S. Composition and origin of the Çaldağ oxide nickel lateritic deposit,
W. Turkey. Miner. Depos. 2009, 44, 581–595. [CrossRef]
12. Roqué-Rosell, J.; Mosselmans, J.F.W.; Proenza, J.A.; Labrador, M.; Galí, S.; Atkinson, K.D.; Quinn, P.D.
Sorption of Ni by “lithiophorite–asbolane” intermediates in Moa Bay lateritic deposits, eastern Cuba.
Chem. Geol. 2010, 275, 9–18. [CrossRef]
Minerals 2019, 9, 51 22 of 25

13. Thorne, R.; Roberts, S.; Herrington, R. The formation and evolution of the Bitincke nickel laterite deposit,
Albania. Miner. Depos. 2012, 47, 933–947. [CrossRef]
14. Thorne, R.L.; Herrington, R.; Roberts, S. Climate change and the formation of nickel lateritic deposits. Geology
2012, 40, 331–334. [CrossRef]
15. Fu, W.; Yang, J.W.; Yang, M.L.; Pang, B.C.; Liu, X.J.; Niu, H.J.; Huang, X.R. Mineralogical and geochemical
characteristic of a serpentinite-derived laterite profile from East Sulawesi, Indonessia:Implications for the
lateritization process and Ni supergene enrichment in the tropical rainforest. J. Asian Earth Sci. 2014, 93,
74–88. [CrossRef]
16. Al-Khirbash, S. Genesis and mineralogical classification of Ni-laterites. Oman Mountains. Ore Geol. Rev.
2015, 65, 199–212. [CrossRef]
17. Putzolu, F.; Balassone, G.; Boni, M.; Maczurad, M.; Mondillo, N.; Najorka, J. Mineralogical association and
Ni-Co deportment in the Wingellina oxidetype laterite deposit (Western Australia). Ore Geol. Rev. 2018, 97,
21–34. [CrossRef]
18. Ratié, G.; Garnier, J.; Calmels, D.; Vantelon, D.; Guimaraes, E.; Monvoisin, G. Nickel distribution and
isotopic fractionation in a Brazilian lateritic regolith: Coupling Ni isotopes and Ni K-edge XANES.
Geochim. Cosmochim. Acta 2018, 230, 137–154. [CrossRef]
19. Mudd, G.M. Global trends and environmental issues in nickel mining: Sulfides versus laterities. Ore Geol. Rev.
2010, 38, 9–26. [CrossRef]
20. Aiglsperger, T.; Proenza, J.A.; Lewis, J.F. Critical metals (REE, Sc, PGE) in Ni laterites from Cuba and the
Dominican Republic. Ore Geol. Rev. 2016, 73, 127–147.
21. Golightly, J.P. Progress in understanding the evolution of nickel lateritics. In The Challenge of Finding New
Mineral Resources—Global Metallogeny, Innovative Exploration, and New Discoveries; Goldfarb, R.J., Marsh, E.E.,
Monecke, T., Eds.; Society of Economic Geologists Special Publication; Society of Economic Geologists:
Littleton, CO, USA, 2010; Volume 15, pp. 451–485.
22. Roqué-Rosell, J.; Villanova-De-Benavent, C.; Proenza, J.A. The accumulation of Ni in serpentines and
garnierites from the Falcondo Ni-laterite deposit (Dominican Republic) elucidated by means of µXAS.
Geochim. Cosmochim. Acta 2017, 198, 48–69. [CrossRef]
23. Fu, W.; Zhang, Y.M.; Pang, C.J.; Zeng, X.W.; Huang, X.R.; Yang, M.L.; Shao, Y.; Henry, L. Garnierite
mineralization from a serpentinite-derived lateritic regolith, Sulawesi Island, Indonesia: Mineralogy,
geochemistry and link to hydrologic flow regime. J. Geochem. Explor. 2018, 188, 240–256.
24. Villanova-de-Benavent, C.; Proenza, J.A.; Gali, S.; Garcia-Casco, A.; Tauler, E.; Lewis, J.F.; Longo, F. Garnierites
and garnierites:Textures, mineralogy and geochemistry of garnierites in the Falcondo Ni-laterite deposit,
Dominican Republic. Ore Geol. Rev. 2014, 58, 91–109. [CrossRef]
25. Ilyas, A.; Kashiwaya, K.; Koike, K. Ni grade distribution in laterite characterized from geostatistics,
topography and the paleo-groundwater system in Sorowako, Indonesia. J. Geochem. Explor. 2016, 165,
174–188. [CrossRef]
26. Quesnel, B.; Veslud, C.L.C.D.; Boulvais, P.; Gautier, P.; Cathelineau, M.; Drouillet, M. 3D modeling of the
laterites on top of the Koniambo Massif, New Caledonia: Refinement of the per descensum lateritic model
for nickel mineralization. Miner. Depos. 2017, 52, 1–18. [CrossRef]
27. Myagkiy, A.; Truche, L.; Cathelineau, M.; Golfier, F. Revealing the conditions of Ni mineralization in the
laterite profiles of New Caledonia: Insights from reactive geochemical µtransport modelling. Chem. Geol.
2017, 466, 1–18. [CrossRef]
28. Qiao, F.G.; Zhu, J.Y.; Tian, Y.L. Nickel resources distribution in the World and nickel deposits in Yunnan
Province, China. Yunnan Geol. 2005, 24, 95–401.
29. Wang, S.W.; Sun, X.M.; Liao, Z.W.; Qu, W.J.; Jiang, X.F.; Li, Y.C. Platinum group elements and Re-Os isotope
geochemistry of harzburgites from Caiziyuan nickel depost in Huili County of Sichuan Province and its
geological significance. Miner. Depos. 2013, 32, 515–532.
30. Zhang, Q.; Zhou, D.J.; Li, X.Y.; Chen, Y.; Huang, Z.X.; Han, S.; Jia, X.Q.; Dong, J.Q. Characterics and Genesises
of Shuanggou Ophiolites, Yunnan Province, China. Acta Petrol. Sin. 1995, 11, 190–202.
31. Mo, X.X.; Pan, G.T. From Tethys to the formation of the Qinghai Tibet Plateau: Constrained by tectono
magmatic events. Earth Sci. Front. 2006, 6, 43–51.
32. Liu, J.L.; Tang, Y.; Song, Z.J. The Ailaoshan Belt in Western Yunnan: Tectonic Framework and Tectonic
Evolution. J. Jilin Univ. 2011, 41, 1285–1303.
Minerals 2019, 9, 51 23 of 25

33. Fang, W.X.; Hu, R.Z.; Xie, G.Q.; Su, W.C. Tectonolithostratigraphic units of the Ailaoshan area in Yunnan,
China, and their implications of tectonic evolution. Geotecton. Metall. 2002, 26, 28–36.
34. Yunnan bureau of Geology and Mineral Exploration. Regional Geology of Yunnan Province; Geological
Publishing House: Beijing, China, 1990.
35. Yin, A.; Harrison, T.M. Geologic evolution of the Himalaya-Tibetan orogen. Annu. Rev. Earth Planet. Sci.
2000, 28, 211–280. [CrossRef]
36. Deng, X.D.; Li, J.W.; Vasconcelos, P.M.; Cohen, B.E.; Kusky, T.M. Geochronology of the Baye Mn oxide
deposit, southern Yunnan Plateau: Implications for the late Miocene to Pleistocene paleoclimatic conditions
and topographic evolution. Geochim. Cosmochim. Acta 2014, 139, 227–247. [CrossRef]
37. Golightly, J.P. Geology of Soroako nickeliferous lateritic deposits, In International Lateritic Symposium, 2nd ed.;
Evans, D.J.I., Shoemaker, R.S., Veltman, H., Eds.; AIME: New York, NY, USA, 1979; pp. 38–56.
38. Cluzel, D.; Vigier, B. Syntectonic Mobility of Supergene Nickel Ores of New Caledonia (Southwest Pacific).
Evidence from Garnierite Veins and Faulted Regolith. Resour. Geol. 2008, 58, 161–170. [CrossRef]
39. Foose, M.P. Nickel–Mineralogy and Chemical Composition of Some Nickel-Bearing Laterites in Southern Oregonand
Northern California; Bulletin; US Government Printing Office: Washington, DC, USA, 1992; pp. 1–24.
40. Sufriadin. Mineralogy, Geochemistry, and Leaching Behavior of the Soroko Nickeliferous Laterite Deposits, Sulawesi,
Indonesia; Gadjah Mada University: Yogyakarta, Indonesia, 2013.
41. Tauler, E.; Proenza, J.; Gali, S.; Lewis, J.F.; Labrador, M.; Garcia-Romero, E.; Suarez, M.; Longo, F.; Bloise, G.
Ni-sepiolite-falcondoite in garnierite mineralization from the Falcondo Ni-lateritic deposit, Dominican
Republic. Clay Miner. 2009, 44, 435–454. [CrossRef]
42. Traoré, D.; BeauvaIs, A.; Chabaux, F.; Chantal, P. Chemical and physical transfers in an ultramafic rock
weathering profile: Part 1. Supergene dissolution of Pt-bearing chromite. Am. Miner. 2008, 93, 22–30.
[CrossRef]
43. Nesbitt, H.W.; Young, G.M. Early Proterozoic climates and plate motions inferred from major element
geochemistry of lutites. Nature 1982, 299, 715–717. [CrossRef]
44. Hill, I.G.; Worden, R.H.; Meighan, I.G. Yttrium: The immobility-mobility transition during basaltic
weathering. Geology 2000, 28, 923–926. [CrossRef]
45. Cathelineau, M.; Quesnel, B.; Gautier, P.; Boulvais, P.; Couteau, C.; Drouillet, M. Nickel dispersion and
enrichment at the bottom of the regolith: Formation of pimelite target-like ores in rock block joints (Koniambo
Ni deposit, New Caledonia). Miner. Depos. 2016, 51, 271–282. [CrossRef]
46. Fritsch, E.; Juillo, F.; Dublet, G.; Fonteneau, L.; Fandeur, D.; Martin, E.; Caner, L.; Auzende, A.L.;
Grauby, O.; Beaufort, D. An alternative model for the formation of hydrous Mg/Ni layer silicates
(‘deweylite’/’garnierite’) in faulted peridotites of New Caledonia: I. Texture and mineralogy of a paragenetic
succession of silicate infillings. Eur. J. Miner. 2016, 28, 295–311. [CrossRef]
47. Skarpelis, N. Lateritization processes of ultramafic rocks in Cretaceous times: The fossil weathering crusts of
mainland Greece. J. Geochem. Explor. 2006, 88, 1–3. [CrossRef]
48. Wang, H.Z.; Chu, X.C.; Liu, B.P. Palaeogeography of China; Map Publishing House: Beijing, China, 1985.
49. Liu, D.S.; Zheng, M.P.; Guo, Z.T. Initiation and evolution of the Asian monsoon system timely coupled with
the ice-sheet growth and the tectonic movements in Asia. Quat. Sci. 1998, 3, 194–204.
50. Du, W.R. Geological characteristics and formation of the Tertiary lignite in Yunnan Province. Yunnan Geol.
1982, 1, 234–245.
51. Liu, R.X.; Xie, G.H.; Zhou, X.H.; Chen, W.J.; Fan, Q.H. Tectonic environments of Cenozoic volcanic rocks in
China and characteristics of the source regions in the mantle. Chin. J. Geochem. 1995, 14, 289–302. [CrossRef]
52. Wang, S.J. Palaeoenvironmental change of the ancient Nihewan Lake area-Sr isotope evidence from
Xiaodukou foraminifera. Acta Geochim. 1996, 15, 105–112.
53. Xu, J.X. Palynology, Paleovegetation and Paleoclimate of Neogene Central-Western Yunnan, China. Ph.D.
Thesis, Graduate School of the Chinese Academy of Sciences, Shenzhen, China, 2003.
54. Wu, J.Y.; Sun, B.N.; Xie, S.P.; Lin, Z.C.; Yan, D.F.; Xiao, L. Two Neogene Machilus (Lauraceae) fossils leaves
from Tengchong, Yunnan Province and its paleoenvironmental significance. Geol. J. China Univ. 2008, 14,
90–98.
55. Wang, P.X. Neogene stratigraphy and paleoenvironments of China. Palaeogeogr. Palaeoclimatol. Palaeoecol.
1990, 77, 315–334. [CrossRef]
Minerals 2019, 9, 51 24 of 25

56. Ding, Z.L.; Yu, Z.; Rutter, N.W.; Liu, T.S. Towards anorbital time scale for Chinese loess deposits. Quat. Sci. Rev.
1994, 13, 39–70. [CrossRef]
57. Clemens, S.C.; Murray, D.W.; Prell, W.L. Nonstationary phase of the Plio-Pleistocene Asian monsoon. Science
1996, 274, 943–948. [CrossRef]
58. Clift, P.D.; Hodges, K.V.; Heslop, D.; Hannigan, R.; Van Long, H.; Calves, G. Correlation of Himalayan
exhumation rates and Asian monsoon intensity. Nat. Geosci. 2008, 1, 875–880. [CrossRef]
59. Li, J.W.; Vasconcelos, P.; Zhang, W.; Deng, X.D.; Duzgoren-Aydin, N.; Yan, D.R.; Zhang, J.Q.; Hu, M.A.
Timing and duration of supergene mineralization at the Xinrong manganese deposit, western Guangdong
Province, South China: Cryptomelane 40Ar/39Ar dating. Miner. Depos. 2007, 42, 361–383. [CrossRef]
60. Jiang, F.C.; Wu, X.H. Late Cenozoic tectonic movement in geomorphologic boundary belt of southeastern
Qinghai-Xizang Plateau. J. Chengdu Univ. Technol. 1998, 25, 162–168.
61. Guo, Z.T.; Yao, X.F.; Zhao, X.T.; Wei, L.Y. A tropical paleosol at high elevation in the Yulong Mountains and
its implication on the uplift of the Tibetan Plateau. Chin. Sci. 2001, 46, 69–73. [CrossRef]
62. Anand, R.R.; Paine, M. Regolith geology of the Yilgarn Craton, Western Australia: Implications for
exploration. Aust. J. Earth Sci. 2002, 49, 3–162. [CrossRef]
63. Grant, J.A. The isocon-diagram—A simple solution to Gresens’ equation for metasomatic alteration.
Econ. Geol. 1986, 81, 1976–1982. [CrossRef]
64. Burns, R.G. Mineralogical Applications of Crystal Field Theory; Cambridge University: Cambridge, UK, 1993;
p. 551.
65. Baumgartner, L.P.; Olsen, S.N. A least square approach to mass transport calculations using the isocon
method. Econ. Geol. 1995, 90, 1261–1270. [CrossRef]
66. Amundson, R. Soil formation. Treatise Geochem. 2003, 5, 1–35.
67. Brown, D.J.; Helmke, P.A.; Clayton, M.K. Robust geochemical indices for redox and weathering on a granitic
lateritic landscape in Central Uganda. Geochim. Cosmochim. Acta 2003, 67, 2711–2723. [CrossRef]
68. Berger, A.; Frei, R. The fate of chromium during tropical weathering: A lateritic profile from Central
Madagascar. Geoderma 2014, 213, 521–532. [CrossRef]
69. Ma, J.L.; Wei, G.J.; Xu, Y.G.; Long, W.G.; Sun, W.D. Mobilization and re-distribution of major and trace
elements during extreme weathering of basalt in Hainan Island, South China. Geochim. Cosmochim. Acta
2007, 71, 3223–3237. [CrossRef]
70. Gong, Q.J.; Deng, J.; Yang, L.Q.; Zhang, J.; Wang, Q.F.; Zhang, G.X. Behavior of major and trace elements
during weathering of sericite–quartz schist. J. Asian Earth Sci. 2011, 42, 1–13. [CrossRef]
71. Gresens, R.L. Composition-volume relations of metasomatism. Chem. Geol. 1967, 2, 47–65. [CrossRef]
72. Brimhall, G.H.; Dietrich, W.E. Constitutive mass-balance relations between chemical composition, volume,
density, porosity and strain in metasomatic hydrochemical systems: Results on weathering and pedogenesis.
Geochim. Cosmochim. Acta 1986, 51, 567–587. [CrossRef]
73. Barker, W.W.; Welch, S.A.; Banfield, J.F. Geomicrobiology: Interactions between microbes and minerals.
In Reviews in Mineralogy, 2nd ed.; Banfield, J.F., Nealson, K.H., Eds.; Biogeochemical Weathering of Silicate
Minerals; Mineralogical Society of America: Washington, DC, USA, 1997; Volume 35, pp. 391–428.
74. Gleeson, S.A.; Butt, C.R.M.; Elias, M. Nickel laterities: A review. Econ. Geol. 2003, 4, 12–18.
75. Retallack, G.J. Lateritization and bauxitization events. Econ. Geol. 2010, 105, 655–667. [CrossRef]
76. Golightly, J.P. Nickeliferous lateritic deposits. Econ. Geol. 1981, 75, 710–735.
77. Dublet, G.; Juillot, F.; Morin, G.; Fritsch, E.; Fandeur, D.; Ona-Nguema, G. Ni speciation in a new caledonian
lateritic regolith: A quantitative x-ray absorption spectroscopy investigation. Geochim. Cosmochim. Acta 2012,
95, 119–133.
78. Dublet, G.; Juillot, F.; Morin, G. Goethite aging explains Ni depletion in upper units of ultramafic lateritic
ores from New Caledonia. Geochim. Cosmochim. Acta 2015, 160, 1–15.
79. Carvalho-E-Silva, M.L.; Ramos, A.Y.; Tolentino, H.C.N.; Enzweiler, J.; Netto, S.M.; Alves, M.D.C.M.
Incorporation of Ni into natural goethite: an investigation by X-ray absorption spectroscopy. Am. Mineral.
2003, 88, 876–882. [CrossRef]
80. Llorca, S.M. Metallogeny of supergene cobalt mineralization, New Caledonia. Aust. J. Earth Sci. 1993, 40,
377–38582.
81. Llorca, S.; Monchoux, P. Supergene cobalt minerals from New Caledonia. Can. Miner. 1991, 29, 149–161.
Minerals 2019, 9, 51 25 of 25

82. Lambiv, D.G.; Gleeson, S.A. Petrography, mineralogy, and geochemistry of the Nkamouna serpentinite:
Implications for the formation of the Cobalt-Manganese Laterite Deposit, Southeast Cameroon. Econ. Geol.
2012, 107, 25–41.
83. Lambiv, D.G.; Gleeson, S.A.; Schofield, P.F. Mineralogical characterization of the Nkamouna Co–Mn lateritic
ore, southeast Cameroon. Miner. Depos. 2013, 48, 155–171. [CrossRef]
84. Manceau, A.; Llorca, S.; Calas, G. Crystal chemistry of cobalt and nickel in lithiophorite and asbolane from
New Caledonia. Geochim. Cosmochim. Acta 1987, 51, 105–113. [CrossRef]
85. Elias, M.; Donaldson, M.J.; Giorgetta, N. Geology, mineralogy, and chemistry of lateritic nickel-cobalt
deposits near Kalgoorlie, Western Australia. Econ. Geol. 1981, 76, 1775–1783. [CrossRef]
86. Scott, K.M.; Pain, C.F. Regolith Science; CSIRO: Dordrecht, The Netherlands; Collingwood, Australia, 2008.

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