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Ore Geology Reviews 80 (2017) 103115

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Ore Geology Reviews

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Hydrothermal mineralization in the sandstonehosted Hangjinqi


uranium deposit, North Ordos Basin, China
Long Zhang a,, Chiyang Liu a,, Mostafa Fayek b, Bailin Wu a, Kaiyu Lei a, Xiaoni Cun a, Li Sun a
a
State Key Laboratory of Continental Dynamics, Department of Geology, Northwest University, Xi'an 710069, China
b Department of Geological Sciences, University of Manitoba, Winnipeg R3T 2N2, Canada

article info abstract

Article history: Tabulartype uranium ore deposits (the Hangjinqi and Daying deposits) have recently been found in the Middle
Received 27 March 2016 Jurassic Zhiluo Formation, north of the Ordos Basin, China. Petrographic observations, the chemical composition
Received in revised form 14 June 2016
Accepted 16 June 2016
of U minerals determined by EMPA and fsLAICPMS, whole rock geochemistry and the microthermometric
Available online 29 June 2016 study of uid inclusions have been integrated to characterize the genetic conditions of the U mineralization in
the Hangjinqi sandstonehosted deposit. Two different groups of U minerals have been identied. One group in-
cludes cofnite(I) associated with vanadiumrich micas. Cofnite(I) is enriched in vanadium (V) and devoid of
iron (Fe) and yttrium (Y) and has a LREEenriched chondritenormalized REE pattern. The U minerals of this
Keywords: group are similar to meteoric uid inltration related deposits. The second group has coeval cofnite(II) and
Sandstonehosted uranium deposit coarsely crystalline calcite cement. Cofnite(II) is enriched in Y and Fe and depleted in V and is marked by a
Ordos Basin
Hydrothermal mineralization
at chondritenormalized REE pattern, which is compatible with typical hydrothermal genetic deposits with
Cofnite highsalinity mineralizing uids. The temperature and salinity of the primary aqueous inclusions in the ore
In situ analyses stage calcite are 120180 C and 8.0016.34% (eq. wt% NaCl), respectively. These mineral assemblages, temper-
atures and salinities indicate that the Hangjinqi deposit was affected by two distinct types of orebearing uids:
lowsalinity meteoric waters and highsalinity hydrothermal uids. The meteoric uids event began at 97
5 Ma with the titling of the northern Ordos Basin and the uplift of the Hetao region to the north. Hydrothermal
U mineralization occurred since 39 2 Ma with the rifting of the Hetao graben. Thus, the previous biogenic
model for the U mineralization should be modied in the uraniferous region of the north Ordos Basin.
2016 Elsevier B.V. All rights reserved.

1. Introduction bacterial activity can be directly related to U mineralization in sand-


stone deposits.
Hydrothermal uid ow has been recognized from uid inclusions
The genesis of sandstonehosted uranium deposits is generally con- and mineralogical studies in some sandstonehosted U deposits, such
sidered to be the interaction of epigenetic oxidizing uranylbearing as the Niger deposits (Pagel et al., 2005; Nie et al., 2010) and the
uids with reducing agents within permeable sandstones, where solu- Dongsheng deposit from the Ordos basin, China (Xiao et al., 2004). Hy-
ble U(VI) can be reduced to insoluble U(IV) by detrital plant debris, hu- drothermal pyrite has also been found using in situ sulfur isotope anal-
mates, hydrocarbons and suldes (Curiale et al., 1983; Hansley and yses of pyrite from rollfront U deposits in the Lake Eyre Basin, Australia
Spirakis, 1992; Spirakis, 1996; Cai et al., 2007a). The abiological reduc- (Ingham et al., 2014). However, a hydrothermal uid event with tem-
tion of U(VI) by these reductants is kinetically inhibited under low tem- peratures in excess of 100 C contradicts biogenic U reduction because
perature conditions (Nakashima et al., 1984; Disnar and Sureau, 1990; bacterial activity would be limited above 80 C (Machel, 2001). To
Lovley and Phillips, 1992). However, Lovley et al. (1991, 1993) reported date, there is no direct evidence that demonstrates whether hydrother-
that bacteria can enzymatically couple U(VI) reduction to organic mat- mal uids participated in the oreforming processes in sandstone
ter oxidation in experimental studies. In addition, biogenic mineraliza- hosted U deposits. Consequently, most genetic models for sandstone
tion has been identied in natural sandstonehosted U deposits (Min hosted U deposits exclude the role of hydrothermal uids (Adams,
et al., 2005; Cai et al., 2007a, 2007b; Jiang et al., 2012). Therefore, 1991).
In recent years, the Hangjinqi, Nalinggou and Daying U deposits
were discovered when wells drilled for gas and coal exploration pro-
duced radioactive samples in the northern Ordos Basin (Figs. 1 and 2).
In addition to the previously discovered Dongsheng deposit, the area

Corresponding authors at: State Key Laboratory of Continental Dynamics, Department


of Geology, Northwest University, Xi'an, Shaanxi 710069, China.
E-mail addresses: longz_1988@126.com (L. Zhang), lcy@nwu.edu.cn (C. Liu).

http://dx.doi.org/10.1016/j.oregeorev.2016.06.012
0169-1368/ 2016 Elsevier B.V. All rights reserved.
104 L. Zhang et al. / Ore Geology Reviews 80 (2017) 103115

Fig. 1. Structural map of the Ordos Basin and its adjacent regions (modied after Liu et al., 2005). 13. Shanxi graben; 4. Weihe graben; 5. Yinchuan graben; 6. Hetao graben; 7. Bohai bay
Basin; 8. Erlian Basin; 9. Yin'gen Basin; 10. Bayanhot Basin; 11. Liupanshan Basin; 12. Xiji Basin; 13. Qinshui Basin; 14. Ningwu Basin; 15. Datong Basin. This map shows the location of ab
crosssection presented in Fig. 2B.

has become one of the most uraniferous regions in China. Previous stud- 2006). Moreover, the broad range of 34S compositions ( 39.2 to
ies of the Dongsheng deposit are debated. Cai et al. (2007a, 2007b) pro- + 15.2) of pyrite occurring in the host sandstone of the Dongsheng
posed that the U mineralization was synchronous with sulfate reduction deposit likely indicates a complex formation mechanism for the pyrite
and petroleum oxidation by sulfatereducing bacteria. Their work em- (Zhang et al., 2006), and not only by bacterial sulfate reduction (BSR),
phasized biogenetic mineralization and similar to other studies on although accurate in situ sulfur isotope analyses are still needed.
other sandstonehosted deposits in sedimentary basins in northern These studies indicate that hydrothermal uids may have played a
China including the Yili and Erlian basins (Min et al., 2005; Bonnetti et role in the formation of U deposits of the northern Ordos Basin. Howev-
al., 2015), which belong to the Central Asia uraniferous province. How- er, it is uncertain whether it is related to U mineralization, and it is dif-
ever, Xiao et al. (2004) reported U minerals in association with coarsely cult to explain the contradictory relationship with biogenetic ore
crystalline hydrothermal calcite from the Dongsheng deposit. The ho- forming processes and the higher temperature hydrothermal uids
mogenization temperatures for the primary aqueous inclusions in the (Cuney, 2010).
calcite mainly range from 90 to 150 C and are higher than the maxi- The trace element composition of U minerals, especially the rare
mum temperature of 70 C for Ubearing sandstones at the maximum earth elements (REEs), has become an increasingly important tool
burial depth calculated from basin thermal modeling (Ren et al., for determining the genetic conditions of U deposits (Bonhoure et
L. Zhang et al. / Ore Geology Reviews 80 (2017) 103115 105

Fig. 2. A. Geological map of the northern Ordos Basin, showing the locations of the Hangjinqi, Daying and Dongsheng deposits. B. Cross section of the northern Ordos Basin.

al., 2007; Mercadier et al., 2011a, 2011b; Depin et al., 2013; Frimmel 2. Geological setting
et al., 2014). Mercadier et al. (2011b) and Frimmel et al. (2014) com-
pared the REE patterns in Uoxides from different types of U deposits
worldwide and demonstrated that genetically different deposits dis- 2.1. The Ordos Basin
play different REE patterns. Lach et al. (2013) proposed that LAICP
MS compared to SIMS has more benets for determining the REEs in The Ordos Basin is located in north central China, covers an area of
Uoxides, including fewer mass interferences and better reproduc- 250,000 km2 and contains various energy resources (oil, gas, coal and
ibility and sensitivity. Their study shows that in situ measurements U). It is a topographic plateau surrounded by several mountain belts:
of REE by LAICPMS can obtain good results using nonmatrix the Yinshan belt (Daqingshan and Langshan mountains) to the north;
matched external calibrators and U as an internal standard. In addi- Taihangshan mountains to the east; Qinling mountains to the south;
tion, femtosecond (fs) LAICPMS has recently been considered and Liupanshan, Helanshan and Zhuozishan mountains to the west
one of the most advanced techniques for in situ elemental analyses, (Fig. 1). A series of grabens developed between those mountains and
which provides signicantly reduced matrix effects, higher spatial the Ordos Basin, including the Hetao graben to the north, the Shanxi
resolution and greater analytical sensitivity than traditional LA graben to the east, the Weihe graben to the south and the Yinchuan gra-
ICPMS (Fernndez et al., 2007; Shaheen et al., 2012). In this study, ben to the west. The MesozoicCenozoic nonmarine Ordos Basin devel-
we analyzed the geochemical composition of cofnite, including oped on the Paleozoic North China platform on a basement of Archean
the REE concentrations, in the Hangjinqi U deposit using highpreci- and Proterozoic continental crust. The stratigraphy of the basin in the
sion femtosecond (fs) LAICPMS and electron microprobe analysis Paleozoic consisted of Cambrian and Ordovician carbonates, experi-
(EMPA). Combined with petrography, uid inclusions and whole enced a regional depositional hiatus and erosion from the Middle Ordo-
rock geochemistry studies of the host sandstone, we determine the vician to the Early Carboniferous and contained Upper Carboniferous
physicalchemical characteristics of the oreforming uids, deter- Permian coalbearing uvialdeltaic clastics and minor shallow marine
mine whether hydrothermal uids participated in the metallogenic carbonates. The Triassic through Middle Jurassic strata consist of uvial
process and constrain the age of the U mineralization. and lacustrine sandstones, shales, mudstones and coals. The Upper Ju-
rassic strata are only distributed on the western margin of the Ordos
106 L. Zhang et al. / Ore Geology Reviews 80 (2017) 103115

Basin (Liu et al., 2006; Ritts et al., 2009), which mainly consist of alluvial abundant carbonaceous debris (Fig. 4C), but in some ores, detrital
fan conglomerates. Most parts of the basin experienced a short period of plant materials is rare (Fig. 4D).
uplift and erosion during Late Jurassic to the earliest Cretaceous. The
Lower Cretaceous strata are comprised of uvial and eolian red beds
(composed of conglomerates, sandstones, mudstones and evaporates). 3. Sampling and methods
The entire basin has been uplifted and formed a plateau since the Late
Cretaceous. Cenozoic strata occur within the grabens along its periphery One hundred and fty drill core samples were collected from 32
and are comprised of alluvial, uvial and lacustrine clastics. holes. Polished thin sections were selected for petrographic and miner-
alogical studies using optical microscopy (transmitted and reected
light) and scanning electron microscopy (SEM) in the backscattered
electron mode equipped with an energy dispersive Xray spectrometer
(EDS). Small goldcoated blocks of the sandstone samples were exam-
ined under a SEM (FEI Quanta 400 FEG) equipped with an EDS in
2.2. Deposit geology order to identify the clay minerals. The chemical compositions of select-
ed cofnite grains were determined using a JEOL JXA8230 EMPA at the
The Hangjinqi U deposit was discovered by the North China Petro- Xi'an Center of Geological Survey, China. The analytical conditions were
leum Company of Sinopec. To the northeast, the Nalinggou deposit bor- a 15 kv acceleration voltage, a 20 nA probe current, a 1 to 5 m beam di-
ders the Hangjinqi deposit and was discovered by the China National ameter depending on the grain size, a 10 s counting time for the major
Nuclear Corporation (CNNC). The two deposits are connected and are elements, 20 s for the minor elements and 40 s for the trace elements.
collectively called the Hangjinqi deposit. The deposit is located in the In situ REE analysis of selected coarsegrained cofnite (N 30 m)
northern Ordos Basin approximately 60 km to the west of Ordos city were performed using a Plasma multicollector ICPMS (Nu Instruments,
and 25 km to the south of the Hetao graben (Fig. 2), where the strata Wrexham, UK) connected to a femtosecond laser system (NWR UPfemto,
display a southwestdipping monocline. The deposit is hosted within ESI, USA) at the State Key Laboratory of Continental Dynamics, North-
the Middle Jurassic Zhiluo Formation and is positioned over a depth in- west University, China. The analytical conditions were a 266 nm output
terval between 300 and 750 m below the surface. The Jurassic and older wavelength, 10 to 20 m laser spot size, 2 Hz pulse repetition frequency,
strata crop out to the northeast of the deposit (Fig. 2). The Middle Juras- and argon and helium were used as the carrier gases. For details of the
sic strata consist of the Yanan, Zhiluo and Anding Formations. The instrumental parameters, see Chen et al. (2014). Each individual analy-
Zhiluo Formation unconformably overlies the coalbearing Yanan For- sis consisted of background collection for 25 s, sample signal acquisition
mation and conformably underlies the Anding Formation. The Anding for 50 s and a wash time of 40 s. The REE compositions were calibrated
Formation has been entirely eroded in some areas, and the Lower Creta- using NIST SRM 610 as an external calibrator, and the U measured by
ceous directly overlies the Zhiluo Formation. The Zhiluo Formation is di- EMPA as an internal standard.
vided into an upper member and a lower member. The upper member is The sandstone samples were powdered in an agate mill to b 200
composed of purple to red mudstone, siltstone, sandstone and minor mesh for wholerock analysis. Major and trace elements compositions
grayish green sandstone deposited in an arid meandering uvial and la- were measured by Xray Fluorescence (Rigaku RIX 2100 spectrometer)
custrine system. The lower member is mainly composed of gray, grayish and ICPMS (Agilent 7500a with a shield torch) at the State Key Labora-
green coarse to mediumgrained sandstone (Fig. 3) with abundant car- tory of Continental Dynamics, Northwest University, China. Analyses of
bonaceous debris and was deposited in a humid or hemihumid braid- US Geological Survey standards BHVO1 (basalt), BCR2 (basalt), and
ed uvial environment. The presence of calcite veins records high AGV1 (andesite) indicated that the precision and accuracy were better
temperature uid activity in the Hangjinqi deposit (Fig. 4A). The grayish than 5% for the major elements and often 10% for the trace elements and
green sandstone consists of chloritizedbiotite and little carbonaceous REEs.
debris. Moreover, residual brownish red and yellow sandstone occurs Double polished thick sections (100m thick) were prepared
within the green sandstone (Fig. 4B), which indicates that the red oxi- from coarsely crystalline calcite cement Ubearing sandstone.
dized zone was reduced by hydrocarbons from the deep basin (Li et Microthermometric data of uid inclusions in calcite were acquired
al., 2007). The main ore bodies are mostly tabular in shape and only oc- using a Linkam THMS600 heating and freezing stage at the State
casionally occurring as rollfronts, occurring in the lowermember Key Laboratory of Continental Dynamics, Northwest University,
Zhiluo Formation. The orehosting sandstone generally is gray adjacent
to the upper green sandstone zone (Fig. 3) and is associated with

Fig. 3. Cross section showing tabular shape ore bodies in the Hangjinqi deposit, modied from CNNC (unpublished data).
L. Zhang et al. / Ore Geology Reviews 80 (2017) 103115 107

Fig. 4. Drill cores from the Hangjinqi deposit. A = calcite veins in sandstone; B = graygreen sandstone and unreduced red sandstone; C = U ore associated with detrital plant debris; D =
U ore with poor carbonaceous debris. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

China. Salinities of aqueous uid inclusions were calculated from nal (red and green sandstone away from the ore zone) and poorly altered
icemelting temperatures using the equations of Bodnar (1993). original gray sandstone. Chlorite generally occurs as an alteration prod-
With the complex multistage mineralization and necrystalline U uct of biotite and is especially prevalent in the graygreen sandstone
minerals in the Hangjinqi deposit, we used EMPA dating to constrain the (Fig. 5B). Illite and interstratied clay minerals are rarely recognized
age of mineralization because of its advantage in spatial resolution. In in the sandstones of different colors, which were generally formed by
order to enhance the accuracy of the chemical age, a longer counting the transformation of eogenetic minerals with increases in burial
time (Pb for 100 s and U and Th for 60 s) and higher probe current depth and temperature (Worden and Morad, 2003). Calcite cement in
(40 nA) were performed. The chemical ages for cofnite were calculated the Zhiluo Formation occurs in two forms: microcrystalline (Fig. 5C)
using the equation of Bowles (1990): and coarsecrystalline (Fig. 5D). The microcrystalline calcite generally
represents meteoric uids related to early diagenesis (Morad, 1998).
In some samples, the preore calcite has been recrystallized to a medi-
um size by later hydrothermal uids (Fig. 5C). The coarsecrystalline
calcite cement represents later hot basinal uid circulation, where
Pb U 0:99276 e1t 1 0:007196 e2t 1 Th e3t 1 twophase aqueous uid inclusions with relative high homogenization
temperatures were observed in the adjacent Dongsheng deposit (Xiao
where 1, 2 and 3 represent the decay constants of 238U et al., 2004). U minerals occur mostly in the form of cofnite (Fig. 6A
(0.000155125 Ma 1), 235U (0.00098485 Ma 1) and 232Th F) associated with pyrite. In some cases, Clausthalite (PbSe) is intimate-
(0.000049475 Ma 1), respectively. The equation can be solved with ly associated with cofnite (Fig. 6F).
an iterative method. A time increment of 0.1 Ma was used in the itera- The Ubearing sandstone can be classied into two end member
tion calculation. groups based on diagenetic mineral assemblages. Group(I) is character-
ized by cofnite, vanadiumrich micas and minor vanadiumrich chlo-
rite with abundant pore spaces in the host sandstone (Fig. 6A and B).
Group(II) cofnite occurs with coarse calcite cement and with few
4. Results pore spaces (Fig. 6C and D).

4.1. Mineral assemblage

The lowermember Zhiluo Formation sandstone in the Hangjinqi


deposit is an immature, moderately to poorly sorted, angular to suban-
gular lithic arenite, in which the detrital grains consist of quartz (16% to
31.8%), feldspar (10.7% to 26.7%) and rock fragments (20.8% to 45.5%).
The rock fragments are composed of tuff, granite, quartzite, schist, 4.2. Chemical composition of the uranium minerals
phyllite, slate and sandstone. Micas, largely biotite (1.8% to 9.2%), are
identied.
Two chemical distinct groups of U minerals were identied corre-
The clay minerals are mainly smectite, kaolinite and chlorite. Smec-
sponding to their different mineral assemblages mentioned above. The
tite is the dominant clay mineral and commonly occurs as thick coats on
cofnite(I) in group(I) is enriched in V2O3 ranging from 1.42 to
detrital grains (Fig. 5A). Porelling kaolinite can be observed in most
5.65 wt% and devoid of FeO (b0.37 wt%) and Y2O3 (below the detection
orehosting sandstone but has a lower content in the oxidized zone
limit) (Table 1). Cofnite(II) in group(II) coexisting with coarsecrystal-
line calcite cement has low V2O3 (b0.23 wt%), and higher FeO and Y2O3
108 L. Zhang et al. / Ore Geology Reviews 80 (2017) 103115

Fig. 5. SEM and thinsection photomicrographs showing the diagenetic minerals in the host sandstone. A = smectite coating along detrital grains; B = chloritized biotite; C =
microcrystalline calcite cement; D = coarsecrystalline calcite cement.

contents than the rst group, ranging from 1.18 to 2.67 wt% and 2.21 sandstone (3115030 ppm) with the highest ratio of V to U, which is
8.98 wt%, respectively. Cofnite together with the calcite cement that in excess of 0.5 (Table 3). The V contents are mostly lower than
experienced partial dissolution (Fig. 6E) is geochemically similar to 100 ppm in the HREEenriched orehosting sandstone, which is similar
cofnite(I). The UO2 content of cofnite(II) is 50.5965.09 wt%, which to the Upoor wall rocks. The content of U in the HREEenriched ore
is relatively lower than cofnite(I), which is 66.4079.20 wt%. In addi- bearing sandstone is lower than that in the LREEenriched sandstone.
tion, the analytical totals of cofnite(II), which range from 84.69 to Calcite cement in the HREEenriched sandstone likely leads to the
88.65 wt%, are lower than cofnite(I), which are 89.0896.59 wt%. The high contents of Ca and LOI.
ThO2 content is below the detection limit in both types of cofnite.
The REE compositions for the cofnite analyzed by fsLAICPMS
are given in Table 2. The cofnite is highly enriched in REEs, with total
REE concentrations ranging from 2.40 to 6.21 wt%. Two REE patterns
were identied for the two different petrographically and chemically
distinct cofnite groups. Cofnite(I) displays a strong enrichment in 4.4. Fluid inclusions in the calcite cement
light REEs (LREEs), which was 2 orders of magnitude more than the
heavy REEs (HREEs) (LREE/HREE = 94.80239.42). Cofnite(II) The uid inclusions in the coarsecrystalline calcite cement of
is much more enriched in REEs (4.136.21 wt%) and HREEs relative to orebearing sandstone are mainly twophase aqueous and occur as
cofnite(I), with LREE/HREE ranging from 0.79 to 1.27, showing isolated populations (Fig. 9A and B). These primary uid inclusions
relatively at REE patterns (Fig. 7). The HREE enrichment in cofnite(II) exhibit euhedral regular to subspherical irregular shapes, and the
is coincident with the high content of Y analyzed by EMPA. These ele- sizes range from 5 to 20 m. Coupled with the previous uid inclu-
ments have closer ionic radii (Shannon, 1976) and display similar geo- sion data of the deposit (Zhang et al., 2015), the homogenization
chemical behaviors. temperatures of the aqueous inclusions range from 120 to 180 C,
and most of the values range from 140 to 160 C (Fig. 9C). The nal
icemelting temperatures range from 5.1 to 12.4 C, which
equate to salinities of 8.00 to 16.34 wt% NaCl (Fig. 9D). Few lowsa-
linity inclusions were observed.

4.3. Whole rock geochemistry

The trace elements analysis shows that the Ubearing sandstone is 4.5. Chemical ages of uranium minerals
distinctly enriched in total REEs (Table 3), which ranges from 144 to
439 ppm and averages of 227 ppm, compared with the unmineralized
sandstone (REE = 80.391.0 ppm). It is likely that U minerals con- To better understand the oreforming processes associated with the
tributed to the high REE contents of the whole rocks, because no other Hangjinqi deposit, it is essential to determine the age of U mineraliza-
REErich minerals in the mineralized sandstone were identied relative tion. Typical samples representing different groups of U minerals were
to the Upoor sandstone. In general, the Ubearing sandstone exhibits selected to determine the age of U mineralization by EMPA, and cofnite
two UCCnormalized REE distribution patterns: LREEenriched and grains containing clausthalite were avoided for analysis. The chemical
HREEenriched (Fig. 8), coincident with the in situ REE analysis of U Pb age of cofnite(I) ranges from 97 to 0 Ma (Fig. 10), which suggests
minerals. Some samples have REE patterns between the LREEenriched that cofnite continuously precipitated or continued to lose Pb during
and HREEenriched ore sandstones, which may reect a mixing of the that period. Cofnite(II) has younger ages beginning at 39 2 Ma. It
two different groups. Vanadium also varied by a large amount in the should be noted that Pb in a large number of cofnite grains was
two distinct groups and is enriched in the LREEenriched orebearing below the limit of detection. This implies the dissolution and
reprecipitation of the cofnite occurred recently (b1 Ma).
L. Zhang et al. / Ore Geology Reviews 80 (2017) 103115 109

Fig. 6. Backscattered electron images displaying the uranium mineralization and associated minerals from the Hangjinqi deposit. A = cofnite associated with pyrite in high porosity
sandstone; B = Vrich micas associated with cofnite; C and D. Cofnite and pyrite crystallization associated with coarse calcite cement; E. Cofnite in calcite with partial dissolution;
F = Coexistence clausthalite and cofnite. Qtz = quartz; Py = pyrite; Cof = cofnite; Pl = Plagioclase; Cal = calcite; Cau = Clausthalite.

Table 1
Representative EMP analysis for cofnite in the Hangjinqi deposit (bdl = below detection limit; n.a. = not analyzed).

Type Cofntie(I) Cofnite(II)

Analysis no. HJQ191 HJQ192 HJQ201 HJQ791 HJQ792 HJQ793 HJQ361 HJQ362 HJQ61 HJQ62 HJQ71 HJQ72 HJQ1115

Na2O (wt%) 0.07 0.01 0.06 0.10 0.12 0.06 0.09 0.02 0.02 0.07 0.04 0.01 0.16
MgO 0.03 0.05 bdl 0.03 0.03 bdl 0.06 0.05 bdl 0.04 bdl 0.02 0.08
Al2O3 0.43 1.61 0.97 0.89 0.66 0.79 0.44 0.57 1.50 0.65 1.30 0.78 1.48
SiO2 14.16 19.78 10.64 13.36 14.27 8.54 4.58 11.41 21.63 9.96 17.47 8.79 20.89
Y2O3 bdl bdl bdl bdl bdl bdl bdl bdl 8.98 5.70 5.36 4.88 2.21
P2O5 0.74 0.12 0.06 0.14 0.48 n.a 0.25 n.a 0.99 n.a n.a 0.48 n.a
CaO 3.79 2.15 2.56 3.25 2.99 2.06 1.13 2.22 1.77 2.53 2.14 2.59 2.04
TiO2 bdl 0.01 bdl 0.33 0.13 0.08 bdl 0.17 0.03 bdl bdl 0.02 0.39
FeO 0.01 0.12 0.06 0.15 0.16 0.17 0.29 0.37 2.67 2.00 2.62 1.75 1.18
UO2 69.19 66.64 72.59 74.34 66.40 79.20 77.74 73.46 50.59 62.62 59.17 65.09 57.52
PbO bdl 0.01 0.02 0.32 0.14 1.03 0.30 0.59 0.07 0.33 0.17 0.28 bdl
ThO2 bdl bdl bdl bdl bdl bdl bdl bdl bdl bdl bdl bdl bdl
K2O 0.17 0.20 n.a 0.22 0.19 0.20 0.19 0.29 0.17 0.18 0.19 0.26 0.17
Cr2O3 0.11 bdl 0.01 0.14 0.10 0.08 0.06 0.12 0.04 bdl 0.03 bdl 0.09
MnO 0.07 0.07 0.19 0.30 0.16 0.63 0.58 0.10 0.03 0.38 0.16 0.55 bdl
V2O3 5.14 1.83 2.44 3.02 3.25 1.42 5.65 3.23 bdl 0.23 bdl bdl 0.07
Total 93.91 92.60 89.60 96.59 89.08 94.26 91.36 92.60 88.49 84.69 88.65 85.50 86.28
110 L. Zhang et al. / Ore Geology Reviews 80 (2017) 103115

Table 2
Representative REE concentrations for cofnite analyzed by fsLAICPMS in the Hangjinqi deposit (in ppm).

Type Cofntie(I) Cofnite(II)

Analysis no. HJQ191 HJQ196 HJQ197 HJQ201 HJQ202 HJQ791 HJQ71 HJQ72 HJQ212 HJQWD21 HJQWD22

La 18,830 14,654 12,812 17,084 16,826 14,651 3733 2715 2177 3308 3430
Ce 8325 8676 9881 10,809 12,429 8632 10,302 8902 6073 11,129 12,504
Pr 216 240 355 275 386 233 1586 1493 1007 1656 2094
Nd 695 709 689 778 1238 608 7455 7264 5453 8015 9627
Sm 69 127 66 116 175 50 3448 3257 2495 3508 4322
Eu 14 32 12 28 42 7 1231 1250 1071 1313 1585
Gd 53 107 55 94 135 46 5282 4799 4591 5253 6158
Tb 7 12 6 11 15 4 966 906 1171 1159 1372
Dy 39 61 33 52 78 21 6827 6244 7187 8102 8909
Ho 7 12 7 11 15 4 1445 1338 1632 1828 1997
Er 20 31 18 29 42 12 3844 3614 4374 4837 5323
Tm 3 4 2 4 5 2 481 433 528 612 637
Yb 24 25 16 30 33 10 2576 2545 3153 3552 3648
Lu 4 4 3 4 5 2 373 330 417 474 493
REE 28,306 24,694 23,955 29,325 31,424 24,282 49,549 45,090 41,329 54,746 62,099
LREE 28,149 24,438 23,815 29,090 31,096 24,181 27,755 24,881 18,276 28,929 33,562
HREE 157 256 140 235 328 101 21,794 20,209 23,053 25,817 28,537
LREE/HREE 179.29 95.46 170.11 123.79 94.80 239.42 1.27 1.23 0.79 1.12 1.18

5. Discussion 1990; Wanty et al., 1990; Meunier, 1994). Similar to U, V mobility is


dominantly controlled by the redox condition, and high valence V(V,
IV) are easily transported in the oxidized environment and are reduced
5.1. Genetic condition of ore formation to insoluble V(III) form. The vanadium likely originated from the disso-
lution of FeTi oxides and precipitated in association with U by the re-
Based on petrography and trace element analysis, there are two dis- duction of microbiogenic H2S or other reducing agents (Wanty et al.,
tinct U mineralizing events associated with the Hangjinqi deposit, 1990). The Vrich micas, Vbearing cofnite and chlorite assemblages
which are different from typical proposed models for the formation of indicate that the vanadium was mostly incorporated into authigenic
tabular or rollfront deposits. micas, cofnite and clays during ore formation. Various models have
The coexistence of V and U in group(I) is a common feature of tabu- been proposed for the typical tabulartype VU deposits on the
lartype VU deposits in the Colorado Plateau, USA (Northrop et al.,

Fig. 7. Chondritenormalized REE patterns of cofnte from the Hangjinqi deposit compared with various types deposits in the world (data from Mercadier et al., 2011b; Lach et al., 2013;
Frimmel et al., 2014). Chondrite normalization values from Anders and Grevesse (1989).
L. Zhang et al. / Ore Geology Reviews 80 (2017) 103115 111

Table 3
Major and trace elements concentrations of wholerock samples in the Hangjinqi deposit.

Ubearing sandstone Upoor sandstone

Type Group(I) Group(II) Mixing group Gray Red Green

Sample HJQ19 HJQ20 HJQ36 HJQ58 HJQ4 HJQ5 HJQ6 HJQ15 HJQ21 HJQ107 HJQ106 HJQ197 HJQ1

SiO2 (wt%) 73.14 73.41 60.12 72.71 46.82 50.17 45.92 52.70 73.38 68.41 74.31 74.00 73.80
TiO2 0.35 0.31 0.47 0.42 0.24 0.40 0.22 0.27 0.46 0.84 0.28 0.25 0.29
Al2O3 12.74 12.70 10.25 12.86 8.43 11.05 8.71 9.76 12.32 12.60 12.54 12.02 12.38
TFe2O3 2.72 2.71 5.59 2.07 12.97 4.17 4.38 3.78 2.70 3.67 2.19 2.01 2.12
MnO 0.06 0.06 0.08 0.08 0.27 0.40 0.31 0.40 0.04 0.09 0.07 0.03 0.03
MgO 1.22 1.19 0.88 0.96 0.97 1.54 0.59 1.26 1.21 1.23 0.96 1.33 1.39
CaO 0.61 0.59 3.77 1.60 10.50 12.24 15.08 13.92 0.78 1.61 0.87 0.91 0.78
Na2O 1.79 1.81 1.68 2.21 1.26 1.29 1.42 1.68 1.77 2.11 2.14 1.93 1.58
K2O 3.51 3.51 2.85 3.52 2.17 2.40 2.38 2.55 3.17 2.97 3.51 3.34 3.35
P2O5 0.08 0.08 0.08 0.08 0.09 0.10 0.05 0.08 0.09 0.14 0.06 0.08 0.09
LOI 3.56 3.20 11.39 2.97 14.89 16.16 19.56 13.12 3.60 4.99 2.79 4.24 4.45
Total 99.78 99.57 97.16 99.48 98.61 99.92 98.62 99.52 99.52 98.66 99.72 100.14 100.26
Sc (ppm) 6.84 6.30 6.31 7.52 5.17 8.58 4.02 4.02 7.77 8.84 5.89 5.64 6.63
V 1033 1092 5030 311 52.6 90.5 159 56.1 45.8 1735 41.3 36.3 33.9
Cr 71.6 37.5 70.8 50.2 36.6 56.1 36.2 106 41.4 60.1 35.5 32.4 35.2
Co 45.2 53.1 7.56 9.03 32.6 16.5 46.3 22.4 45.6 8.24 5.96 43.8 28.0
Ni 36.9 18.4 20.3 11.8 34.5 20.8 42.7 51.5 14.7 14.9 10.4 12.0 14.6
Ga 17.5 16.8 17.5 12.2 10.4 15.4 10.6 8.95 15.1 15.7 13.4 12.6 13.6
Rb 92.7 89.1 90.7 93.8 54.9 65.5 61.6 59.4 81.9 80.6 84.2 82.7 82.2
Sr 292 291 338 317 207 234 325 217 259 306 305 386 326
Y 9.97 10.3 21.2 11.0 107 104 191 84.7 39.5 28.1 8.82 7.19 8.21
Zr 120 119 199 116 82.7 147 118 50.4 217 272 232 109 102
Nb 8.51 7.57 9.96 8.30 3.98 7.37 6.05 3.85 9.60 14.1 6.08 5.19 5.95
Cs 1.59 1.49 3.37 1.46 0.95 1.42 0.98 1.07 1.36 2.21 1.35 1.47 1.14
Ba 1011 1055 1015 1080 604 585 738 758 895 940 1941 1911 956
Hf 2.85 2.86 4.81 3.30 2.09 3.25 2.24 1.37 4.71 6.16 5.26 2.63 2.48
Ta 0.59 0.50 0.56 0.54 0.28 0.42 0.34 0.51 0.67 0.81 0.37 0.35 0.39
Pb 12.5 16.4 67.5 45.4 33.4 8.78 20.3 61.2 10.3 12.9 12.9 13.0 10.1
Th 4.87 3.95 5.38 4.22 3.02 4.10 3.35 3.75 6.29 7.78 3.98 3.12 3.53
U 3260 3731 7170 2660 631 391 866 287 975 2043 5.89 0.58 0.75
La 51.0 69.6 166 63.6 21.6 34.5 33.9 33.6 24.3 58.9 19.5 17.3 21.1
Ce 132 90.4 222 152 41.9 63.4 61.3 50.8 60.5 101 38.8 36.5 39.5
Pr 10.2 5.56 9.30 11.4 5.60 7.63 7.73 5.81 8.42 8.07 4.50 3.87 4.45
Nd 25.9 19.5 24.5 30.6 24.8 30.3 33.7 27.4 36.9 28.0 16.1 14.2 16.3
Sm 2.99 3.16 3.55 3.61 7.37 7.78 11.3 6.28 9.32 5.15 2.73 2.36 2.69
Eu 0.89 0.98 1.13 0.86 3.21 2.96 4.34 2.50 2.70 1.37 0.94 0.84 0.87
Gd 3.02 2.81 3.01 2.83 10.3 11.1 19.3 6.99 8.22 4.96 2.19 1.87 2.09
Tb 0.32 0.33 0.47 0.53 1.81 1.96 3.74 2.03 1.02 0.69 0.29 0.25 0.27
Dy 1.74 1.82 2.97 1.75 11.7 13.3 26.6 16.2 5.28 3.95 1.60 1.34 1.53
Ho 0.32 0.34 0.65 0.39 2.49 2.83 5.91 3.29 0.97 0.80 0.31 0.25 0.28
Er 0.95 0.99 2.01 1.11 6.73 8.01 17.1 8.36 2.61 2.23 0.87 0.70 0.84
Tm 0.13 0.14 0.31 0.21 0.83 1.09 2.32 1.35 0.33 0.33 0.13 0.10 0.12
Yb 0.91 0.94 2.14 0.78 4.55 6.26 13.7 7.27 2.06 2.02 0.86 0.64 0.80
Lu 0.14 0.14 0.35 0.15 0.71 0.95 2.09 1.09 0.31 0.31 0.13 0.10 0.12
REE 231 197 439 270 144 192 243 173 163 218 89.0 80.3 91.0
LREE 223 189 427 262 104 147 152 126 142 202 82.6 75.1 84.9
HREE 7.53 7.51 11.9 7.75 39.1 45.5 90.8 46.6 20.8 15.3 6.38 5.25 6.05
LREE/HREE 29.61 25.19 35.80 33.82 2.67 3.22 1.68 2.71 6.83 13.24 12.94 14.30 14.03

Colorado Plateau. Northrop et al. (1990) and Wanty et al. (1990) sug- model. Hansley and Spirakis (1992) and Spirakis (1996) emphasized
gested that tabular ore formed at the interface between Ubearing me- the role of organic matter in the genesis of VU deposits. They believed
teoric water and sulfaterich basinal brine; this is called the interface that epigenetic amorphous organic matter precipitated in tabular layers

Fig. 8. Upper continental crust normalized wholerock REE patterns for Ubearing sandstone and unmineralized rock. UCC normalization values from Taylor and Meclennan (1985).
112 L. Zhang et al. / Ore Geology Reviews 80 (2017) 103115

Fig. 9. Photomicrographs (A, B), histograms of homogenization temperatures (C) and salinities (D) of primary aqueous uid inclusions (PI) in coarsely crystalline calcite cement from ore
bearing sandstone.

at the solution interfaces and that these organic matter (humate) layers reect the conditions of the mineralizing uids. To our knowledge,
then built reduced chemical environments for mineralization when U there are no in situ analyses of REE patterns for cofnite because
bearing oxidized water was transported to the redox interface. Sanford cofnite often occurs as a trace, negrained alteration mineral in
(1992, 1994) proposed a hydrological model in which an interface was many deposits (Janeczek and Ewing, 1991, 1992; Fayek et al., 1997,
formed between the local and regional groundwater discharges and 2002; Deditius et al., 2008). However, cofnite often forms under simi-
found a strong association between tabular U deposits and freshbrine lar conditions as uraninite. Cofnite forms when the activity of Si is high
water interfaces. In general, tubulartype VU deposits formed by and uraninite forms when the activity of Si is low (Guo et al., 2015).
redox reaction at the boundary between U and Vbearing meteoric Cofnite often coexists with uraninite and both minerals are U4+ min-
water and tabular shaped organic matter layer or basinal brine. erals (Janeczek and Ewing, 1991, 1992; Fayek et al., 1997, 2002). There-
The REE composition of uranium oxides is controlled mainly by the fore, REE patterns in uraninite are likely a good proxy for REE patterns in
physicalchemical characteristics of the mineralizing uids (Mercadier cofnite, and can be used to infer formational conditions for cofnite.
et al., 2011b). The REE3 + in cofnite (USiO4nH2O) have ionic radii The chondritenormalized REE patterns of cofnite(I) in the Hangjinqi
close to that of U4+ (Shannon, 1976), which allows REE3+ to easily sub- deposit are similar to veintype and typical rollfront type deposits
stitute for U4+ during cofnite crystallization (Hansley and Fitzpatrick, (Fig. 7), such as the Tortkuduk deposit in the ChuSarysu Basin, Kazakh-
1989; Deditius et al., 2008). The REE pattern of cofnite can possibly stan (Mercadier et al., 2011b). The U deposits that show strong LREE en-
richment are characterized by lowsalinity mineralizing uids that
inherited the REE pattern of the host rocks and were not fractionated
during source leaching, REE transport and U mineral crystallization
(Mercadier et al., 2011b). This also suggests that the genesis of
cofnite(I) in the Hangjinqi deposit was probably epigenetic and related
to the lowsalinity and lowtemperature meteoric waters. However,
dolomite in adjacent sandstones and evaporites in underlying strata,
typical features of the tabular deposits of the Colorado (Northrop et
al., 1990), were not observed in the Hangjinqi deposit, which indicates
that the VU mineralization from the Hangjinqi deposit is not similar
to the VU mineralization from Colorado deposits.
The orestage calcite of Group(II) formed at higher temperatures
(120 to 180 C) and from moderate to highsalinity uids. The at
REE patterns of cofnite(II) are similar to synmetamorphic deposits
(Fig. 7), which form from hightemperature and highsalinity mineral-
izing uids. Mercadier et al. (2011b) suggested that salinity (ligands)
plays a critical role in REE fractionation during REE mobilization and de-
position. Mclennan and Taylor (1979) reported that U and HREE were
selectively transported in a hydrothermal uid with soluble carbonate
complexes from a metamorphic related deposit in Australia. Experi-
mental studies have shown that a solution with a high concentration

Fig. 10. Chemical Pb ages for cofnite in the Hangjinqi deposit.


114 L. Zhang
L. Zhang
et al.et/ al.
Ore/ Ore
Geology
Geology
Reviews
Reviews
80 (2017)
80 (2017)
103115
103115 113

U ore
of carbonate
(later thanions
39 can 2 Ma)
decrease
are coincident
REE adsorption
with theontoagessandstone
of the forma- and changes in reductionoxidation conditions of the uid can cause U to be
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UPb isotopic
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mate-
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This study was funded by the Natural Science Foundation of China


(grant No. 41330315), the China Geological Survey Project (grant No.
12120114009201), and the National Basic Research Program of China
(grant No. 2015CB453000). The North China Petroleum Company,
Sinopec and the Geological Team No. 208, BOG, CNNC are rstly ac-
knowledged for their help during sampling. We thank Prof. Honglin
Yuan and Dr. Zhian Bao from Northwest University for providing help
during fsLAICPMS experiments. We also express our thanks to
Ningchao Zhou from Xi'an Center of Geological Survey for his assistance
with EMPA and chemical dating. We are very grateful to Editor-in-Chief
Prof. Franco Pirajno and two anonymous reviewers for their construc-
tive comments and suggestions on the manuscript.

Fig. 11. Sequence of mineral paragenesis, tectonic event and hydrocarbon migration for the Hangjinqi deposit.
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