3.0 END USES

3.1 End Uses and Sharing

Barium or baryte or barium sulphate is used in many industries for different production processes. Up to 84% of the barite production is used as a weighing agent in oil and gas drilling muds. Drilling muds are pumped down into the borehole during the drilling of oil and gas wells to lubricate and cool the drill bit, float cuttings out, seal rock strata that are porous, and apply hydrostatic pressure to prevent water from filling the borehole1. Barite is an excellent drilling mud additive because it is soft, easily crushed and milled, virtually chemically inert, has no magnetic effects, is not abrasive, and has a high specific gravity that can withstand high down-hole pressure2.

Crushed barite mixed with water and other materials is used as drilling mud additive. Then this mixture is pumped in to the drill hole of the oil well which will counteracts the force of the released oil and gas due to the high weight of this mixture. Due to this counteract of drilling mud the high explosiveness of the released oil and gas from the ground is controlled making safe environment for the drill rig operators to work.

End Uses Elasticity: On average in World Barite consumption over 84% is used for drilling application (Fig_1 – Summary of World Barite Consumption). Thus the consumption in the drilling mud usually fluctuates as it is directly dependent on the amount of exploration drilling for oil and gas, which in turn depends on the prices of the oil and gas. Thus, a demand short-run of barite to the present end-users specially Oil and Gas industry appears to be inelastic with respect to price due to higher dependency of the industry on Barite . All types of drilling fluids use Barite as a weighting agent with the chemical formula of BaSO4 (Barium Sulfate). The most important application of Barite as a weighting agent for drilling mud are due to increase of the mud density up to 2.5 g/cm3 (21 lb/gal), control the pressure of the formation, stabilization of the borehole, preparation of the solids-laden plugs for well control application3.

Fig-1: Summary of Barite Consumption by Industry 4

Softness, chemical inertness, high brightness, low solubility, high density whiteness and relative cheapness of Barite has become the main reasons for wide application of it in many industries. Some of them are;

• as a filler in paint and plastics• the production of lithophone, which is a high performance white pigment composed of a

Drilling Mud - 84%

Glass, Ceramics, etc (Chemical) - 7%Filler – Car, Rubber & Paint - 9%

mixture of chemically precipitated and calcined zinc sulphide and barium sulphate. Titanium dioxide has largely replaced barytes for this application, but there are still some specialised uses.

• Minor uses as an absorber of gamma and X-ray radiation, e.g. special concrete to shield nuclear and X-ray installations. In the construction industry barites is sometimes added to concrete to increase its density for specialist application. In medicine, it is used to highlight problems within the human body.

• In glass manufactures as a flux and to add brilliance and clarity.• pharmaceutical industry (purified barite, which is radio-opaque, is administered in a

“barium milkshake” or enema prior to gastrointestinal x-rays);• sugar refining;• television and computer screen manufacturing (barite is used in the faceplates and

funnelglass of cathode-ray tubes); • metal casting (barite is used in the mold-release compounds); • vehicle manufacturing (barite is used in the friction products for brake and clutch pads);• food manufacturing (barite can be used as a forming agent); • paper and rubber manufacturing (barite is used as a filler or a weighting agent);• heavy concrete production (barite is used as a radioactive shield);• firework production (barite is used to make the colour green); and, • pond repair (barite is used to stop leaks in lined ponds that cannot be drained).

The above list was generated using information from the following sources: ADMMR, 20015; USGS, 20116; CEPA, 20037; and Code of Federal Regulations (2008)8.

The levels of the impurities in the minerals or elements in the barite has limited its application. Some of the elements in the barite are fluorine, strontium, lead, zinc or iron in considerable amounts and will be reduced by blending or treatment9.

3.2 Future of Barite

Future for Barite is unclear since it is highly dependent on the future of the oil and gas production. Oil has been extracted for 100 years with the discovery of over 41,000 oil fields and expected to be last for another several decades. But these fields are enormously varying with the size and distribution.

3.3 Substitutes for Barite

Most of the industry are investing money on researching to find out possible substitutions for maintaining a sustainable viable production process within their industry. Similarly barite industry have substitutes also. Other similar minerals such as celestite (strontium sulfate) and iron ore are considered as the possible substitutes for the Barite used in Oil and Gas drilling industry10. A German company is producing synthetic iron ore (hematite) which is proving a good substitute for barite. However, these alternatives have yet to be widely used in the oil industry, and barite continues to be the preferred commodity for this application as long as barite production remains strong.

4.0 P4.0 PRODUCTIONRODUCTION

4.1 Geographical Distribution of the Deposits

The world total Barite resources, estimated to 2 billions tons out of which only 740 million tons have been identified, is conceivable for many years of world Barite requirement. The China has become the main producer of Barite for several years due to its richness of the Barite reserves. China reserves more than 40% of the world Barite reserves11.

Fig_3.1- Geographical distribution of major active and inactive Barite mines and significant deposits 12

The geographical distribution of major Barite mines and deposits are illustrated in Fig_3.1 above. There are three major types of Barite deposits; stratiform, vein and residual. Vein deposits were the most reliable deposit in the past which often associated with zinc and lead deposits and residual deposits whereas as at present most production were based on stratiform deposits.

Table-4.1: Major Stratiform Deposits of Barite 13

Country Location Remarks

Western USA NevadaArkansas, Alaska

In siliceous sediments.In siliceous carboniferous sediments.

Canada MacMillan Pass, Anvil Palaeozoic selwyn

Scotland Aberfeldy Proterozoic meta sedimentary rocks

Germany Devonian Shale

Pakistan Mesozoic Carbonates

Russia Primory

The deposits which are formed due to the barite precipitation at or near the seafloor of sedimentary basins are called as stratiform deposits. These deposits occur as large conformable beds within organic- and chert-rich sediments; the beds lack major sulphide minerals and are the largest and most economically significant barite deposits in the geologic record14. The Mangampet deposit in Andhra Pradesh, India is the largest single deposit of this type. Some of major stratiform deposits occur in Cambrian black shales in the Jiangnan region of southern

China and the Qinling region in the Yangtze valley where the latter area contains some whiterite and barytocalcite (BaCa(CO3)2) deposits associated with Barites horizons. Some of the stratiform deposits spread worldwide are tabulated in Table 4.1 above15.

A vein-type deposit is a fairly well defined zone of mineralization, usually inclined and discordant, which is typically narrow compared to its length and depth. Most vein deposits occur in fault or fissure openings or in shear zones within country rock16. Vein type deposits were common in past for production of Barite. Major vein deposits are found in Morocco, USA, Germany and Slovakia. Ballynoe deposit in Ireland produced over 5 million tons of direct shipping Barite during 1963 to 199317.

4.2 Barite Extraction and Processing

4.2.1 Mining

Barite mining process differs based on the type of deposit. Commercial Barite is mined from surface or near-surface deposits by open-pit or underground mining methods. This method of mining is practised in stratiform deposit mining due to formation thickness and feasibility. The ore is drilled , blasted, extracted and transport to mill for processing. Vein deposits are worked by shaft and adits as well as shallow open pits depending on the depth and accessibility18.

4.2.2 Processing

The broken ore is trucked to the processing plant where it may be washed to remove adhering clay and low-grade fines before reduction by crusher to a specified size or finer for further processing. The degree of further processing and concentration depends on the grade of ore, identified end use, and liberation size (i.e., the size at which the barite is essentially free of contaminating impurities)19.

Fig_4.2: Barite Production Process

The concentrated barite may be ground to final size specifications by a suitable milling unit. A 45-micrometre (μm) product is normally specified for drillmud barite; however, a much finer product may be required for other applications such as chemical and pharmaceutical preparations20. Barite used for drilling petroleum wells must be finely ground so that at least 97% of the material, by weight, can pass through a 200-mesh (75-μm) screen, and no more than 30%, by weight can have an effective diameter of less than 6 μm, which is measured using sedimentation techniques. The ground barite must also be dense enough so that its specific gravity is 4.2 or greater, soft enough to not damage the bearings of a tricone drill bit, chemically inert, and contain no more than 250 mg/kg of soluble alkaline salts. A small percentage of iron oxide is allowable21.

4.3 Production of Barite as a Mineral Commodity

4.3.1 World Production

According USGS mineral statistics of 2011 the world’s barite resources in all categories are about 2 billion tons, but only about 740 million tons is identified resources22.

Source: United State Geological Survey

World Barite production was amounted to 7.8 million metric ton in 2011. Up to 84% of the barite production is used as a weighing agent in oil and gas drilling muds. This highlights that the Barite industry closely tied with the Oil and Gas industry. Fig_4.4 illustrates the world Bar ite production from 1950 to 2010.

Fig_4.4: World Barite Production from 1950-2010Source: United States Geological Survey

The apparent increase in barite production between 1950 and 1975 can, in part, be attributed to improved reporting by several countries that are significant producers23. During 1981 there was a boom in the oil exploration industry which caused the considerable increase in the Barite production of around 8.3 million metric tons. Second and third peaks in 1997 and 2008 amounting 6.7 and 8.6 million Mt respectively occurred due to the increase in the oil exploration caused by the increase of the price. During the peak in 1997 the two largest barite producers in China increased production in an effort to consolidate their influence on the world market. These efforts were partly successful because rapid increase in production affect the quality of the product leading a reluctance to buy.

United States ; 6.38%

Algeria; 12.34%

China; 42.54% Germany; 0.43%

India; 13.61%

Mexico; 2.98%

Morocco; 4.25%

Pakistan; 0.43%

Russia; 5.10%Turkey; 1.70%

United Kingdom; 0.04%

Other Countries; 10.21%

CountryReserves Reserves

(in Million tons) (in %)United States 15,000 6.38Algeria 29,000 12.34China 100,000 42.54Germany 1,000 0.43India 32,000 13.61Mexico 7,000 2.98Morocco 10,000 4.25Pakistan 1,000 0.43Russia 12,000 5.10Turkey 4,000 1.70United Kingdom 100 0.04Other Countries 24,000 10.21

Fig_4.3: World Reserves of Barite 2011

1950

1955

1960

1965

1970

1975

1980

1985

1990

1995

2000

2005

2010

0

1,000,000

2,000,000

3,000,000

4,000,000

5,000,000

6,000,000

7,000,000

8,000,000

9,000,000

Source: Data taken from USGS mineral dataFig_4.6: Barite Production in 2002 and 2011

The Fig_4.6 illustrates how the Barite production has been changed in a decade from 2002 to 2011. China and India together were able to produce almost half of the World Barite production out of them almost 40% of the world production is produced by China.

4.3.2 Social, Political, Environmental and Technological Factors that affect the Production and Production Cost

As mentioned in the above chapter on main factor which affect the Barite production is the increase in the oil and gas production since the main consumer of the barite is the gas and oil industry. This effect can be clearly observed by observing the peaks in 1997 and 2008.

Source: World mineral Statistics, British Geological Survey and Baker Hughes Inc (rig count data)Fig_4.5: World Barite Production Compared with the Annual average number of Active Exploration and

Producing oil and Natural Gas Rigs (1975-2003)

The above figure illustrates that the increasing sensitivity of barite production to variation in drill rig activity. Same trend could be observed up to 1986 between Barite production and rig activity because a change in rig activity mirrored by an equivalent change in Barite production. After

1986 the Barite production was sensitive to the rig activity because a small change in rig activity caused a considerable increase with several multiplies in the Barite production. Geopolitical Issues Faced by Major Producers in 2011: In 2011 the Barite production was fuelled by the rapid expansion of the economies of countries such as Brazil, China, and India, the demand for oil and gas has risen rapidly. This increase in demand, plus improvements in technology, has resulted in a substantial increase in worldwide exploration for oil and gas and with it an increase in consumption of barite24. In 2011, the major producer of Barite, China has decreased its production by approximately 11% compared to 2008 peak production but increased export by 12% compared to that of 2010. The decrease in the reserves of some traditional deposits and the combination of strict adherence to the environmental and health regulation causing smaller mines out of business impacted greatly for the decrease in production in China. Natural disaster such as flooding damaged to the Barite production in India decreasing by 1Mt but recovered during summer production25.

4.4 Barite Production, Environment and Sustainable Development

4.4.1 Environment and Health:Barite is not very mobile or bioavailable under most atmospheric, water, or soil conditions and does not undergo photolysis, abiotic, or biotic oxidation to yield barium ions26. Thus the health hazards and environmental hazards caused by Barite are limited compared to other mineral commodities. Information on the environmental fate and behaviour of barite or barium (as barite) is limited because the barium cycle has not been investigated. Most anthropogenic sources of barium emissions release barium (including barite) in particulate form. Atmospheric barium is not widely dispersed27. Although some smaller barium-containing particles may have a residence time in the atmosphere up to a few days, the majority of particles are greater than 10 μm in size and will quickly settle back to land or water28. The residence time of barium-containing particulates in air is a function of barium speciation, the chemical nature of the particulate, and environmental factors (e.g., rainfall). Barium is deposited to land and water through wet and dry deposition. Due to strong affinity of Barium ion to the sulfate ion the solubility of Barite in water is very low. Barite readily forms and precipitates out of the solution. Thus once formed it is very spearingly soluble under neutral pH and oxidation conditions. Barite in soil has very low mobility due to its insolubility and inability to form soluble complexes with humic and fulvic matter29.

As Barite exhibits no evidence of carcinogenicity, developmental toxicity, reproductive toxicity, neurotoxicity, gene mutation, or chronic toxicity related to exposure, it is considered as non-toxic30. However, the barium ion is toxic if in an available form. The toxicity of the barium ion depends on the solubility of the barium compound. The low toxicity of barite to humans and environmental receptors is largely due to its insolubility in water, weak acids, and alcohols.

Several cases were reported on baritosis caused in Barium-exposed workers31. This caused due to inhalation of the barium ore or barium sulfate. The most outstanding feature of baritosis is the intense radiopacity of the discrete opacities, which are usually profusely disseminated throughout the lung fields; in some cases the opacities may be so numerous that they appear confluent. The available human data on baritosis suggest that the accumulation of barium in the lungs does not result in medical disability or symptomatology32. A decline in the profusion and opacity density, suggesting a decrease in the amount of accumulated barium in the lung, has been observed several years after termination of barium exposure. During a investigation carried out examining 8 workers employed for 3.5 to 18 years in a Barite mine and seven of the workers reported no respiratory symptoms; 1 worker reported a slight occasional cough. Pneumoconiosis was detected in the radiographs of 7 workers. Ten of the 11 workers examined in 1961 were re-

examined in 1963 (18 mo later). Two new cases of pneumoconiosis were diagnosed. Thus, 9 of 10 workers exposed to barium sulfate for 1.5 to 19.5 years (mean of 8.2 years) had well-marked baritosis. Three of these workers reported a slight or occasional cough and none had dyspnea33.

4.4.2 Sustainability Approaches:

Most of the mining industries involved with many activities which affect the social, environmental and economical sustainability. But they are supposed to closely adhere to the environmental or social standards, regulations and guidelines on sustaining the ecosystem not only during its operations or processing but also after the production till the end of the life cycle of the product. When consider barite production it is mostly carried out by the governments of the major producing nations, thus they are highly binding to such sustainability initiatives.

Sustainability reporting carried out by the Institute for Studies in Industrial Development in Delhi, India reports that most of the mines are carried out scientific mining other than adhoc methods originating from a systematic approach to mine development and operation and considered it as the first step for ensuring environmental sustainability in mining. Some of the steps involved in scientific mining includes mine planning, mine development and operations, mineral waste management, tailings management and mine closure planning.

The major pollution caused from mine is the air pollution which due to the particulate matter of various sizes and chemical constituents or dusts. Thus dust management at various stages of mining operations is the most important challenge. Some of the reported air quality management practices carried out by the Indian mine sites are34,

• Regular water sprinkling (at intervals) on haul roads, other roads and working areas as well as active overburden dumps.

• Wet drilling and site mixed emulsion for drilling with less noise, vibration and dust in larger mines.

• Dust extractors in the crushing and screening plants, water spraying and dry fog system at the crushing plant.

• Use of covered dumpers and trucks for transportation of ore extracted. • Rehabilitation of waste dumps through vegetation. • Creation of green belts around the mining areas.

Fig_4.6: Rehabilitation of Waste Dumps and Plant NurseriesWater pollution caused due to higher loads of suspended solids through ore-washing at the screening plant, slimes generation in the stockpiles or dumps and erosion over degraded lands. Some of the measures taken by the Indian mine industry to mitigate water pollution are,

• Construction of check dams to harvest rainwater and arrest surface runoffs;• Provision of garland drains around major waste dumps; • Provision of settling ponds at suitable locations and channeling flow of water running

down the hill or dumps to settling ponds.

Further they value the community engagement in the mining process as an positive impact for sustainability objectives. Thus the community development has been considered as a major objective of their sustainability development initiatives and carried out different projects in order to achieve the said initiatives. Construction and maintenance of primary school buildings, construction of wells, tube wells, village tanks and temples, maintenance of some village roads, frequently used by the mining company for its business, and free medical camps and distribution of medicines are some of the measures reported35.

1 Nelson, D.W., S.L. Liu, and L.E. Sommers, 1984. Extractability and Plant Uptake of Trace Elements from Drilling Fluids. Journal of Environmental Quality, 13: 562-566.2 WHO (World Health Organization), 2001. Concise International Chemical Assessment Document 33: Barium and Barium Compounds. Accessed on 05 January 2013 at http://www.inchem.org/documents/cicads/cicads/cicad33.htm.3 http://mineral.eng.usm.my/web%20halaman%20mineral/Baryte.pdf . The website was accessed on 21

December 2012.4 The Barytes Association. Website Access on 05 January 2013 http://www.barytes.org/uses.html 5 ADMMR (Arizona Department of Mines and Mineral Resources), 2001. Prospecting for Barite. Accessed on 10 December 2012 at http://www.admmr.state.az.us/circ4barite.htm. 6 USGS (United States Geological Survey), 2001. Mineral Commodity Summaries 2001. U.S. Geological Survey, U.S. Department of the Interior. Accessed on 12 December 2012 at http://minerals.usgs.gov/minerals/pubs/mcs/2011/mcs2011.pdf. 7 CEPA (California Environmental Protection Agency), 2003. Public Health Goal for Barium in Drinking Water. Prepared by Pesticide and Environmental Toxicology Section, Office of Environmental Health Hazard Assessment, California Environmental Protection Agency. September 2003. Available on-line at http://oehha.ca.gov/water/phg/pdf/Ph4Ba092603.pdf. 8 Code of Federal Regulations, 2008. Accessed on 28 December 2012 https://explore.data.gov/Other/2008-Code-of-

Federal-Regulations-in-XML/hw8m-hfte 9 Bonel, K.A., 2005, Mineral Profile – Barytes, British Geological Survey, 7.10 Bonel, K.A., 2005, Mineral Profile – Barytes, British Geological Survey, 7.11 http://minerals.usgs.gov/minerals/pubs/mcs/2012/mcs2012.pdf Accessed on 05.01.2013.12 Bonel KA. Mineral Profiles Barytes. Natural Environmental Research Council, British Geological Survey. 2005.13 Bonel KA. Mineral Profiles Barytes. Natural Environmental Research Council, British Geological Survey. 2005.14 Torres ME, Bohrmann G, Dube TE, Poole FG. Formation of modern and Paleozoic stratiform barite at cold methane

seeps on continental margins. The Geological Society of America. 2003. Vol. 31 no. 10. pp 897-900

15 Bonel KA. Mineral Profiles Barytes. Natural Environmental Research Council, British Geological Survey. 2005.16 http://earthsci.org/mineral/mindep/depfile/vei_dep.htm#def Accessed on 08.01.2013.17 Bonel KA. Mineral Profiles Barytes. Natural Environmental Research Council, British Geological Survey. 2005.18 Bonel KA. Mineral Profiles Barytes. Natural Environmental Research Council, British Geological Survey. 2005.19 http://www.shibang-china.com/application/barite-mining.html Accessed on 10.01.201320http://mineral.eng.usm.my/web%20halaman%20mineral/Baryte.pdf Accessed on 20.12.201221http://mineral.eng.usm.my/web%20halaman%20mineral/Baryte.pdf Accessed on 20.12.201222 United States Geological Survey. Mineral Commodities Summaries 2012. U.S. Department of the Interior. 201223 Bonel KA. Mineral Profiles Barytes. Natural Environmental Research Council, British Geological Survey. 2005.24 United States Geological Survey. Mineral Commodities Summaries 2012. U.S. Department of the Interior. 2011 25 United States Geological Survey. Mineral Commodities Summaries 2012. U.S. Department of the Interior. 201126 US EPA (United States Environmental Protection Agency), 1991. Barium Sulfate; Toxic Chemical Release Reporting; Community Right-To-Know. Environmental ProtectionAgency, 56 FR 23668. 23 May 1991.27 Alberta Environment. Soil Remediation Guideline for Barit: Environemntal Health and Human Health. Climate

Change, Air and Land Policy Branch, Alberta Environment. 200928 WHO (World Health Organization), 2001. Concise International Chemical Assessment Document 33: Barium and Barium Compounds. Accessed on 12 December 2012 at http://www.inchem.org/documents/cicads/cicads/cicad33.htm.29WHO (World Health Organization), 2001. Concise International Chemical Assessment Document 33: Barium and Barium Compounds. Accessed on 12 December 2012 at http://www.inchem.org/documents/cicads/cicads/cicad33.htm.30 Alberta Environment. Soil Remediation Guideline for Barit: Environemntal Health and Human Health. Climate

Change, Air and Land Policy Branch, Alberta Environment. 200931 http://www.epa.gov/iris/subst/0010.htm Accessed on 11.01.2013.32 http://www.epa.gov/iris/subst/0010.htm Accessed on 11.01.2013.33 http://www.epa.gov/iris/subst/0010.htm Accessed on 11.01.201334 http://planningcommission.gov.in/reports Accessed on 11.01.2013.35 http://planningcommission.gov.in/reports Accessed on 11.01.2013.