World bromine

Situated between the solid and gaseous states as the only non-metallic element liquid at ambient temperature, bromine is sandwiched in the periodic table between the ubiquitous chlorine and the rather rare iodine. In terms of production volumes it is neither a bulk commodity chemical like chlorine, nor a speciality chemical like iodine. And commercially, bromine is beset by uncertainty. Until the 1970s, the major market forbromine was in dibromoethane - a co-additive for leaded petrol. The phase-out of lead in petrol could have spelled the collapse of the bromine industry, but alternative bromine markets developed and the industry both rationalised and flourished. However, although world bromine production continues to increase slowly, fresh environmental concerns have emerged and the industry is once more under threat. Details are given. 19 refs. 

There are a relatively small number of producers of halogenated flame retardants, especially for brominated flame retardants, where three producers account for greater than 80% of world production. Table 10 gives estimates of the volumes of brominated and chlorinated flame retardants used worldwide. Volumes of flame retardants consumed in Japan have been summarized (61). Prices of halogenated flame retardants vary from less than 2.00/kg to as high as 13.00/kg. Cost to the user depends on the level of use of the specific flame retardant and other factors such as the use of stabilizers. 

Not considering the former USSR, world production of iodine was ca 13,500 metric tons in 1992. Japan provided about 45% of the world total, compared to 44% from Chile and 11% from the United States. An annual output of 2300 t from 1976 to 1979 was estimated by the U.S. Bureau of Mines (66) but was revised to 2000 tons in 1981. No official data are available for the former USSR where iodine production is reported to be produced from iodine—bromine brines. Two areas have been mentioned the Neftechalinki field in the Slavianski-Triotskoe area near the Black Sea, and a plant in the Baku area in Azerbaidzhan on the Caspian Sea where ca 1400 metric tons was estimated for 1990 production. 

An average of about 7 ppm of bromine is found ia terrestrial plants, and edible foods contain up to 20 ppm. Among animals the highest bromide contents are found ia sea life, such as fish, sponges, and cmstaceans (44). Animal tissues contain 1—9 ppm of bromide and blood 5—15 ppm. The World Health Organization has set a maximum acceptable bromide iatake for humans at 1 mg/kg of body weight per day. In adult males the bromine content ia semm has been found to be 3.2—5.6 p.g/mL, ia urine 0.3—7.0 p.g/mL, and ia hair 1.1—49.0 p.g/mL. Bromine may be an essential trace element as are the other hahdes (45). 

Figure 3 shows the prices of bromine in tank car quantities from 1976 to 1990. Although the price rose 99% over these years, an average of 5.0% a year, when inflation is taken into account, the price in constant dollars actually fell slightly over that period (51). Estimates of bromine production around the world are shown in Table 3. 

Figure 4 shows U.S. bromine production with respect to bromine production in the rest of the world. Israel, especially, has increased its production in recent years (51,52). Between 1976 and 1990 U.S. production fell from 234,000 to 177,000 metric tons Israel s production increased from 23,000 to 135,000 metric tons over that period. 

The main metals in brines throughout the world are sodium, magnesium, calcium, and potassium. Other metals, such as lithium and boron, are found in lesser amounts. The main nonmetals ate chloride, sulfate, and carbonate, with nitrate occurring in a few isolated areas. A significant fraction of sodium nitrate and potassium nitrate comes from these isolated deposits. Other nonmetals produced from brine ate bromine and iodine. 

In addition to being the most widely used disinfectant for water treatment, chlorine is extensively used in a variety of products, including paper products, dyestuffs, textiles, petroleum products, pharmaceuticals, antiseptics, insecticides, foodstuffs, solvents, paints, and other consumer products. Most chlorine produced is used in the manufacture of chlorinated compounds for sanitation, pulp bleaching, disinfectants, and textile processing. It is also used in the manufacture of chlorates, chloroform, and carbon tetrachloride and in the extraction of bromine. Among other past uses, chlorine served as a war gas during World War I. 

World production of Bra in 1990 was about 438 000 tonnes pa, i.e. about one-hundredth of the scale of the chlorine industry. The main producing countries are (tonnes) USA 177000, Israel 135 000, Russia 60000, UK 28 000, France 18 000 and Japan 15 000. The production capacity of Israel has recently increased almost threefold because of expanded facilities on the Dead Sea. Historically, bromine was shipped in individual 3-kg (net) bottles to minimize damage due to breakage, but during the 1960s bulk transport in monel metal drums (100-kg capacity) or lead-lined tanks (24 or 48 tonnes) was developed and these are now used for transport by road, rail and ship. The price of Bra in tank-car lots was 975/kg in 1990. 

Of major concern are the health and environmental impacts of the abundant chlorinated and brominated hydrocarbons (ref. 2). These materials have numerous industrial applications as pesticides, solvents, propellants, refrigerants, plastics, fire retardants and extinguishers, disinfectants for drinking water, pharmaceuticals and electronic chemicals. Many chemical manufacturers utilize chlorinated and brominated organics as intermediates. It is estimated, for instance, that almost 85 % of the pharmaceuticals produced in the world require chlorine at some stage of synthesis. 

HBCD is a brominated aliphatic cyclic hydrocarbon used as a flame retardant in thermal insulation building materials, upholstery textiles, and electronics. In 2001, the world market demand for HBCD was 16,700 tons, from which 9,500 tons was sold in the EU. These figures make HBCD the second highest volume BFR used in Europe [29], HBCD may be used as an alternative for PBDEs in some applications. To date, there are no restrictions on the production or use of HBCD. As a result of their widespread use and their physical and chemical properties, HBCD are now ubiquitous contaminants in the environment and humans [30, 31]. 

UK breast milk samples are some of the most contaminated with brominated flame retardants in the world, according to... 

It is a well-known fact that a pharmaceutical substance can be prepared by adopting different routes of synthesis based upon the dynamic ongoing research in the field of organic-reaction-mechanisms. Relentless efforts are exerted vigorously by reputed research laboratories across the world to look for shorter routes of synthesis bearing in mind the cost-effectiveness of the final product. For instance diclofenac sodium (an NSAID) can be manufactured by two methods, one using a bromo compound as a starting material while the other is based on a non-bromo compound. Nevertheless, the latter product is more in demand because it is completely devoid of bromine residues in the final product. 

Electrolux is the world s largest producer of powered appliances for kitchen, cleaning and outdoors. They have created comprehensive Environmental Product Declarations (EPDs) for many of their product lines. Information within the product profiles details chemicals that have been banned as well as the percentage and types of materials and how they have improved material choices. Forexample, plastic components do not contain cadmium, lead, mercury or their compounds or chlorinated or brominated flame retardants metal components are not coated with cadmium, chromium, or nickel and metal paints do not contain pigments and additives based on heavy metals. Many Electrolux products are also PVC-free. 

Nokia, the world s largest manufacturer of mobile phones, has committed to phasing out brominated flame retardants (BFRs) and PVC plastic. Chicco, a manufacturer of toys and baby products, will eliminate the use of PVC within threeyears small amounts of this plastic are still used in components, accessories and packaging. 

PVC plastic is the largest end user of phthalates and a significant end userfororganotins and brominated flame retardants with antimony. A phase out of PVC therefore directly reduces use of these hazardous constituents. Alternatives to PVC vary and must be assessed on their chemical profile. Greenpeace has charted the move to PVC alternatives over the last few years and has compiled an extensive database of PVC restrictions world-wide, which is available on line. ... 

Helleday T, Tuominen KL, Bergman A, Jenssen D (1999) Brominated flame retardants induce intragenic recombination in mammalian cells. Mutat Res 439 137-147 Hern J, Feltz HR (1998) Effects of irrigation on the environment of selected areas of the Western United States and implications to world population growth and food production. J Environ Manage 52 353-360... 

Figure 13.7 shows the effective total tropospheric concentration of chlorine from halocarbons from 1992 to 1996 (Montzka et al., 1996a). The concentration peaked in 1994 at 3.0 ppb, but when methyl chloride (CH-,C1) and other chlorinated organics are taken into account, the peak was likely 3.7 ppb. The total tropospheric chlorine concentration in mid-1995 decreased at a rate of approximately 25 ppt per year, in contrast to increases of 110 ppt per year in 1989 (Montzka et al., 1996a Cunnold et al., 1997). Bromine compounds show the same trend. As a result, the stratospheric levels of chlorine and bromine are expected to peak around the year 2000 (Montzka et al., 1996a World Meteorological Organization, 1995,1999). 

Roskill Information Services (1997) Bromine—World Market Overview, London [http //www.roskill.co.uk/bromine.html]... 

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