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Geochemistry and Petrographical Study of Langrial Iron Ore from Tethyan Hazara Area Pakistan, with Emphasis on its Economic Characterization and Depositional Setting

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Geochemistry and Petrographical Study of Langrial Iron Ore from Tethyan Hazara Area

Pakistan, with Emphasis on its Economic Characterization and Depositional Setting

Naghmah Haider1, Sajjad Khan1, Mehboob Ur Rashid1*, Rehan ul Haq Siddiqui2, Jawad Zeb1, Shahid Iqbal3, Asad Khan4, Waqas Ahmad5

1

Geoscience Advance Research Laboratories, Geological Survey of Pakistan, Islamabad, Pakistan 2

BITUMS University, Quetta, Balochistan, Pakistan 3

Department of Earth Sciences, Quaid Azam University, Islamabad, Pakistan 4

Department of Geology, FATA University, Dara Adam Khel, Pakistan 5

National Centre of Excellence in Geology, University of Peshawar, Pakistan

*Email: mehboobgeo89@gmail.com

Received: 18April, 2018 Accepted: 12 July, 2018 Abstract: The Langrial iron ore of Hazara area has been studied in detail at five locations for its geochemistry, genesis and economic potential investigations. A maximum of thirty samples were collected from iron ore bodies at different localities of Bagnotar, Danna Noral, Tatti Maira, Najafpur and Jabri for detailed analysis. The thick bedded iron ore has been deposited in the form of unconformity at Cretaceous-Paleocene boundary sandwiched between Kawagarh and Hangu formations (i.e. Cretaceous-Paleocene boundary). At the base of Hangu Formation variable thickness of these lateritic beds spread throughout the Hazara and Kohat-Potwar plateau. These iron ore bodies are studied by X-Ray Diffraction technique (XRD), X-ray Fluorescence Spectrometry (XRF), Petrographic studies and Scanning Electron Microscope (SEM). This XRD analysis indicated that iron bearing minerals are hematite with intercalation of chamosite, quartz and a proportion of impurities having albite, illite-montmorillonite, kaolinite, calcite, dolomite and ankerite. The X-ray Fluorescence (XRF) results show that total Fe2O3 ranges from 30 to 50% having high silica, while alumina to silica ratio is less than 1. The petroghraphic studies revealed concentration of Langrial iron beds as oolitic hematite nodule having variable concentric to composite structure. A high energy shallow marine depositional environment was deduced for Langrial iron ore, as inferred from SEM and mineralogical data. The overall results show that Langrial iron ore is a low-grade iron ore with average Fe2O3 of 52%, and can be upgraded by applying modern mining techniques to fulfill steel requirements of the country.

Keywords: Geochemistry, petrography, iron ore, Cretaceous-Paleocene boundary, Hazara.

Introduction

Iron ores have great significance in the modern world, because it is used for the extraction of iron which is utilized in making steel and a number of other alloys (Cloud, 1973; Galdon-Sanchez and Schmitz Jr., 2002). Iron ore usually occurs in a number of geological environments from deep seated basic igneous intrusion through late stage hydrothermal igneous, metamorphic and sedimentary environment (Kazmi and Abbas, 2001; Williams et al., 2005). These iron deposits occur in sedimentary formation of Precambrian age as Banded Iron Formation (BIF) ore occurs as oolitic ironstone in Paleozoic to Cretaceous sedimentary successions of the world (Chan, 1992; Konhauser et al., 2002). The occurrences of iron ores are widespread in Pakistan with massive iron ores reported in igneous rocks of Nagarparkar, magmatic type of Balochistan to oolitic iron type of Khyber Pakhtunkhwa mainly composed of magnetite and hematite (Ahsan et al., 2008; Chan, 1992; Siddiqui et al., 1999). The iron ore bodies have been widely reported from Indus platform zone, Foreland sedimentary belt, Himalayan crystalline belt, Ophiolitic thrust belt and Chagai magmatic arc (Kazmi and Abbas, 2001). These deposits are mostly

contact metasomatic and volcanogenic types and concentrated along unconformities. The iron bodies of volcanic type are also reported from Precambrian shield rocks of Chiniot and Sargodha (Butt et al., 1993). In Himalayas Foreland Fold and Thrust Belt (HFFTB) of Pakistan, ironstones of oolitic textures are mainly reported in Mesozoic to early Tertiary formations (Ahmad, 1969; Garzanti, 1993; Hallam and Maynard, 1987). The Langrial iron ore is concentrated on the western limb of crescent shaped Hazara Kashmir Syntaxes (HKS) having trend of North-East to South-East direction (Thakur et al., 2010). The crescent shaped HKS is bounded by Panjal Thrust at North and Main Boundary Thrust (MBT) in south having similar trend of NE-SW direction (Fig. 1a). The oldest rock unit exposed in the area is Hazara slates of Precambrian age uncomformably overlain by sedimentary rocks of Lumshiwal and Kawagarh formations of Cretaceous age (Kazmi and Jan, 1997; Klinger et al., 1967). The grade wise description of Langrial iron ore is analyzed in this study to be utilized in the national asset, strengthen the economy and national treasure. The deposit should attain key importance, if studied for its benefication potential using modern benefication techniques and enrichment

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of iron content.

The main focus of the study is to explain textural characteristics, mineralogy and depositional environment with emphasis on economic characterization of Langrial iron ore of Hazara area.

Study Area

The study area (Langrial Iron Ore) is part of Himalayan Fold and thrust belt, situated at a distance of 35 km south of Abbottabad. The Langrial iron ore is covering an area of 200 km2 extending from Khanpur to Kalabagh cantonment, having estimated reserves of 30 million tonnes iron ore (Kazmi and Abbas, 2001). The study area falls in Survey of Pakistan toposheet no 43G/1 and 43C/13 covering coordinates of Najafpur (33º 50' 32" N, 72º 59' 06" E), Jabri (33º 54' 15" N, 73º 10' 28" E), Danna Noral (33º 56' 32" N, 73º 10' 57" E), Tatti Maira (34º 06' 19" N, 73º 19' 40" E) and Bagnotar (34º 06' 58" N, 73º 20' 20" E) (Fig. 1b). The iron ore bearing beds occur in the shape of oolitic hematite concentrated along Cretaceous-Paleocene unconformity of Kawagarh and Lockhart formations. The Paleocene Lockhart Formation is lying above the ironstone beds and Cretaceous Kawagarh Formation is lying below the ironstone beds (Table 1) (Shah, 2009; Yoshida et al., 1998). The iron ore bodies occur in the shape of isolated bodies due to structural faulting, which dislocates the beds and are also concentrated along the limb of Lockhart limestone anticline. The deposits of Langrial iron ore are spread over 32 km and are of economic

interest, as the grade varies between 30 to 50% at selected locations. The thickness of iron beds change from 8 to 10 meters, as ferruginous hematitic oolitic type ore,with thickness of oolites beds being 12 to 15 feet (Klinger et al., 1967).

Materials and Methods

The study area has been surveyed by taking sample from five sections that are, i.e. Bagnotar, Danna Noral, Tatti Maira, Najafpur and Jabri with total coverage of the area being 32 kilometers for detailed analysis. A total of 30 representative rock samples were collected and analyzed from the study area and orientation of beds were also observed (Table 2). The mineralogical composition of the sample was observed using X-rays Diffraction machine, while elemental analysis was done by X-rays Fluorescence (XRF) spectrometry. The XRD analysis was carried out by crushing and powdering the rock sample and analyzing it through CuK radiation scanning by Panalytical X’ PertPRO Diffractometer with a speed of 0.05 /Sec. The diffracted pattern of each sample was labeled for different mineral composition using XPert software by applying the techniques of curve matching, 2ϴ angle and existing minerals data base. The elemental analysis for all major elements was done by PanalyticalAxios WD-XRF using glass bead mounted sample at a ratio of 1:10 of volatile free sample and lithium tetra borate. The details of petrography, mineralogy and depositional setting was done under camera fitted Nikon made reflected light polarizing microscope at

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magnifications of 200μm. The point and micro structure analysis was performed by using Scanning Electron Microscope (SEM) (Model JEOL JSM 6610LV), while the compositional variations were found out using EDS (OXFORD X-MAX 20mm2). In order to avoid the charging of particles during the observation, carbon coating was well applied to the thin sections.

Table 1. Lithostratigraphic unit of the Hazara- Abbottabad area (modified after Shah, 2009).

Results and Discussion

The mineralogical analysis of all samples from the seven selected sites revealed that the most prominent mineral is hematite, chamosite and quartz with minor impurities of albite, illite-montmorillonite, kaolinite, calcite, dolomite and ankerite. Based on the results of XRD, it is suggested that the hematite nature of the ore is having alteration of chamosite, quartz and clay as gangue minerals. The XRD study has direct influence on commercial value, processing and beneficiation of

ore for consumption. The study of gangue associated with ore is essential in taking steps for beneficiation. The XRD analysis also shows that localities of Danna Noral and Najafpur have high iron content in the range of 40-50%, and such deposit requires little or no beneficiation, while Bagnotar has low hematite content of 20-25% (Fig. 2).

The XRF analysis was performed for major elemental analysis mainly; SiO2, TiO2, Al2O3, Fe2O3, MnO, MgO, CaO, Na2O, K2O, P2O5, Fe, Al/Si and Loss on Ignition (LOI). The elemental analysis of Bagnotar area was compared to Danna Noral, Najafpur, Jabri and Tatti Maira. The elemental analysis for Bagnotar and Tatti Maira shows high silica content within the range of 17-28% and 30-35% while that of others areas are less than 20% (Table 3 , 4). The average Al2O3 is high (12%) while in Fe2O3, Fe content is less (32% & 22%) compared to other locations (Table 3). The elemental analysis also shows that Danna Noral is having high Fe content (45%) followed by Najafpur (39%), Jabri (36%) and Tatti Maira (30%). The calcium content (10%) of Bagnotar area is also high due to its closure to Lockhart limestone. The economic characterization of Bagnotar and other areas are also examined in terms of silica and alumina contents, which show that Bagnotar area is hiving high gangue contents in the form of silica and alumina making it less economical, and more beneficiation will be required compared to other localities (Fig. 3a). The Danna Noral, Najafpur Jabri and Tatti Maira Iron Ores are having high Fe2O3 contents with respect to SiO2 and Al2O3 contents, reaching up to 70% (Fig. 3b). These low grade iron ores can be upgraded to 62% through beneficiation (Muwanguzi et al., 2012). According to Rao et al., (2009) the beneficiation of ore requires crushing, scrubbing and washing to reduce alumina content to make it economical. The beneficiation should require gravity separation as well as magnetic separation of Langrial iron ore deposits. The aluminum to silica (Al/Si) ratio in all samples is less than , which is good for beneficiation (Table 2, 3). The increase of Al/Si ratio (ideally it should be < 1) is having adverse effects on blast furnace and sinter plant, as it corrodes the plant easily and decreases its life time. (Rao et al., 2009). An increase in alumina alone raises the melting point of slug and enhances burden of fuel consumption and decreases its economical outcome.

Table 1. Orientation, type and feature of samples collected in the study area.

Area Orientation Type Geological features

Strike Dip

Bagnotar N10 E 32 SW Chamosite-limonite Overlain and underlain by lockhart formation Jabri N60 E 30 SE Haematitic-limonitic Thin to medium bedded laterite Danna noral N60 E 30 SE Haematitic-limonitic Thin to medium bedded laterite

TatiMaira N30 E 25 SW Latiritic-Chamosite Laterite beds observed

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Fig. 2 Showing XRD pattern by CuK of selected powder samples, dominant peaks are labeled.

Table 2. Showing elemental composition of samples collected from Bagnotar area.

Analysis Bagnotar

B1 B2 B3 B4 B5 B6 Ave

SiO2 20.24 17.32 18.52 28.04 27.46 23.3 22.5

TiO2 0.7 0.45 0.42 0.63 0.79 0.58 0.6

Al2O3 12.44 10.53 10.46 10.98 17.63 11.88 12.3

Fe2O3 48.25 54.21 56.31 45.06 39.45 45.24 48.1

MnO 0.04 0.1 0.08 0.13 0.03 0.03 0.1

MgO 2.58 2.31 2.28 2.27 2 2.01 2.2

CaO 4.12 3.06 2.62 3.07 2.98 2.96 3.1

Na2O 0.23 0.77 0.39 0.31 0.13 0.41 0.4

K2O 0.09 0.1 0.41 0.17 0.21 0.07 0.1

P2O5 1.34 1.41 1.41 1.17 0.7 1.1 1.2

LOI 9.88 9.27 7.36 8.17 9.28 12.43 9.4

Fe 33.73 37.89 39.36 31.5 27.58 31.62 33.6

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Table 3 Showing elemental composition of samples collected from Danna Noral, Najafpur Jabri and Tatti Maira areas.

Fig. 3 Showing iron, aluminum and silica ratios of selected samples collected from northern part i.e. Bagnotar area and southern part including Danna Noral, Najafpur Jabri and Tatti Maira areas.

The petroghraphical studies indicate that iron oxide mineral is mainly composed of hematite with the combination of quartz and chamosite and these results are in conformation with XRD analysis. The study also shows that hematite occurs as replacement of original grain as oolitic nucleus (Fig. 4a), while chamosite occurs as alteration product (Fig. 4d). These ooids are composed of concentric layers having deposition of hematite and iron rich clays, chamosite and in this regard the Langrial iron ore is iron rich chamosite type deposit. The photomicrographs also show that the ratio between hematite and chamosite varies referring to its alteration at different rate of country’s rock. The ooids are of two types and entirely hematite type (Fig. 4c) or

replacement type mostly of chamosite minerals (Fig. 4d). The variable composition of ooids nucleus is composed of iron oxides, quartz, feldspar, other rock fragments and broken fragments of older ooids (Fig. 4b).

The compositional variation of ooids was observed through backscattered image of SEM (Fig. 5) The SEM analysis shows that ooids are of three types, that are concentric or elliptical (Fig. 5a,c,e), composite type (Fig. 5b) and concentric laminated type (Fig. 5d, f). The SEM analysis also shows that Langrial iron ore is deposited in high energy shallow marine environment having limited clastic as some ooids are embedded as nuclei of other ooids (Fig. 5f).

D1

D2

D3

Ave N1

N2

N3

Ave J1

J2

J3

Ave T1

T2

T3

Ave

SiO

2

12.51 12.61 9.75

11.6 21.04 11.37 13.54 15.3 18.72 19.94 18

18.9 35.38 30.76 33.07

33.1

TiO

2

0.84

0.68

0.27

0.6 0.84

0.52

0.55

0.6 0.6

0.57

0.5

0.6 0.54

0.51

0.525

0.5

Al

2

O

3

9.7

10.3

7.62

9.2 18.84 8.47

10.79 12.7 7.31

12.71 9.3

9.8 10.02 10.53 10.275 10.3

Fe

2

O

3

63.93 59.13 72.74 65.3 37.2

69.73 57.75 54.9 52.94 50.58 53.57 52.4 38.82 46.59 42.705 42.7

MnO

0.02

0.02

0.01

0.0 0.04

0.53

0.05

0.2 0.01

0.3

0.23

0.2 0.16

0.09

0.125

0.1

MgO

1.55

1.5

1.19

1.4 4.79

2.65

3.2

3.5 1.78

3.47

3.67

3.0 1.31

1.29

1.3

1.3

CaO

2.29

5.8

1.32

3.1 1.26

3.34

3.54

2.7 1.05

1.09

1.12

1.1 1.79

2.2

1.995

2.0

Na

2

O

0.48

0.25

0.38

0.4 2.11

0

0.18

0.8 1.94

0

1.51

1.2 2.12

0

1.06

1.1

K

2

O

0.02

0.02

0.03

0.0 -

0.01

-

0.0 0.04

-

0.3

0.2 0.02

0.02

0.02

0.0

P

2

O

5

1.53

1.37

0.78

1.2 0.24

0.55

2.41

1.1 0.15

0.3

0.23

0.2 1.08

1.38

1.23

1.2

LOI

7.15

8.32

5.91

7.1 13.65 8.64

7.99

10.1 15.96 13.22 13.67 14.3 8.78

9.33

9.055

9.1

Fe

44.69 41.33 50.85 45.6 26

48.74 40.73 38.5 37.01 35.36 37.28 36.6 27.14 32.57 29.855 29.9

Al/Si

0.77

0.82

0.78

0.8 0.89

0.74

0.79

0.8 0.39

0.65

0.55

0.5 0.28

0.34

0.31

0.3

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Fig.4 Photomicrographs of selected samples collected from the study area showing (a) concentric ooids with hematite and chamosite rich concentric lamination (a, d). Elongated ooids due to early compaction.(b) Nucleus of oolites consists of quartz, feldspars,

hematite and rock fragments(c, d) ooids consist of pure hematite, whereas others are comprised of entirely chamosite

Review on Depositional Settings of Langrial Iron Ore

The hematite-chamosite composition of the deposits indicate intense chemical weathering under humid continental conditions (Boggs, 2009), and that type of conditions prevail in humid equatorial settings (Warwick et al., 1995). Paleo-geographic reconstruction studies indicate that the study area was positioned at equatorial region during the deposition of the Langrial iron ore (Fig. 6) (Yoshida et al., 1998). According to Young, (1989) ooids are representing shallow water agitated environment and such oolitic texture is characteristic of Phanerozoic iron ore deposits. The concentric rings of these ooids having iron minerals (hematite, magnetite) which are formed by chemical replacement of the sedimentary rocks (Tucker, 2009). The warm and humid climate, high relative sea level and

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older Cretaceous paleo-surfaces (Warwick et al., 1995). The intense chemical weathering coupled with tropical climatic conditions initiated production of Fe-rich minerals, an amorphous hydroxide or goethite during the lateralization process. The preservation of these sediments are favored by marine transgression along the continental margin (Yoshida et al., 1998). The high PCO2 , probably associated with the Deccan Trap basalts may have created a stratified ocean with reducing conditions and negative Eh (Schoene et al., 2015). Such conditions favored the deposition of siderite (FeCO3), under reducing conditions and low sulfide activity (PS2) in sediment pore-waters (Harder, 1989). The Deccan trap activity also contributed the release of extra sulfur to the environment, hence the oolitic iron ore accumulated in non-marine brackish environment (Yoshida et al., 1998). According to Schulte et al. (2010) the bacterial decomposition of

organic matter followed by Cretaceous/Paleocene event created anoxic event which favor siderite precipitation. The process of digenesis converted primary ooids into hematite-chamosite ooids through process of consolidation and compaction (Crowe et al., 2007). The formation of chamosite (Mg, Fe)3Fe3(Si3Al)O10(OH)8, is also favored by fluctuating oxic to anoxic conditions due to Deccan trap activity (Schulte et al., 2010). These strong oxidizing conditions provided the opportunity for the hematite precipitation (Tucker, 2009).

These fluctuating conditions and mineralogical composition having hematite, quartz, chamosite and clay minerals show strong agitating and oxidizing environemnt prevailing in shallow marine setting, which must have a strong control on the depositional and early digenetic history of the Langrial iron ore.

Fig. 5 Scanning electron microscopic (SEM) images of the iron ore thin section. (a, c, e) concentric and elliptical ooids (b) composite ooids (d, f) concentric lamination in cortex of the ooids CO is composite ooids, Co is cortex, C is chamosite, H is hematite, M is

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Fig. 6 Inferred paleo-geographic location of Hazara area and Indian subcontinent in early in Paleocene time (Yoshida et

al., 1998).

Conclusion

Langrial iron ore occurs in the basal part of Hangu Formation of Paleocene age mainly of hematitic nature with gangue minerals like quartz, chamosite, minor impurities of albite, illite-montmorillonite, kaolinite, calcite, dolomite and ankerite. The deposits are low-grade iron ore mostly hematite and chamosite in nature and average Fe2O3 content is ≥50%. The Danna Noral deposits are more economical with grade reaching 45% (Fe), 56% (Fe2O3), which require less beneficiation, while deposit of Bagnotar is less economical and more beneficiation should be done, which has average grade of ≤35%. The average grade of Fe and Fe2O3 of Jabri (55% and 35%), Najafpur (53% and 37%) and Tatti Maira (42% and 30%), require little beneficiation. The Al2O3 content of Jabri, Danna Noral, Tatti Maira and Najafpur is less than 10% so most feasible for beneficiation, while in Bagnotar it is 12%. The mineralogical and petrological interpretation shows tthat the deposit was formed under warm humid climate due to oolitic nature or alteration of minerals. The occurrence of ooid fragments as nucleus of other ooids with limited clastic supply and presence of chamosite and quartz indicate high energy shallow marine depositional setting. The Langrial iron ore has aluminum to silica ratio less than 1 which is good for beneficiation. Langrial iron ore is having good economic significance proved by combined petroghraphical, geochemical and mineralogical data and the value can be further increased by the application of modern metallurgical processing and benefication. The presence of variable concentric oolitic layers will lead to more processing and crushing to convert the iron ore to economical form in particular

Langrial iron ore oolitic structure. From all these geochemical and mineralogical analyses, it is inferred that Langrial iron ore beds can be beneficiated economically to a maximum extent through modern techniques of bioleaching and metallurgical techniques.

Acknowledgement

The authors thank Mr. Nazar-ul-Islam, Director General Geological Survey of Pakistan and Ministry of Energy (Petroleum Division), for providing us the opportunity to execute the current project. A special thanks to laboratory facilities and colleagues of Geoscience Advance Research Labs (GARL) Geological Survey of Pakistan for carrying out the analysis of samples.

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Figure

Fig. 1a) Tectonic map of the study area modified after Thakur et al., (2010). b) Location map showing samples position of the study area
Table 1. Orientation, type and feature of samples collected in the study area.
Table 2. Showing elemental composition of samples collected from Bagnotar area.
Table 3  Showing elemental composition of samples collected from Danna Noral, Najafpur Jabri and Tatti Maira areas
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References

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The challenges for individuals with IDDs involve activities of daily living such as dressing, eating, toileting, challenging behavior (meltdown/tantrum/self-injury),

We asked two specific questions: (i) is lean mass more important that fat mass as a determinant of bone mineral density in postmenopausal women; and (ii) given the sampling

tigrinus bites are rare in clinical practice but demon- strated DIC with the fibrinolytic phenotype, which can result in life-threatening injury unless appropriate anti- venom and

Twenty-five percent of our respondents listed unilateral hearing loss as an indication for BAHA im- plantation, and only 17% routinely offered this treatment to children with