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Ingested Nitrate and Nitrite INGESTED NITRATE AND NITRITE INGESTED NITRATE AND NITRITE This monograph focuses on ingested nitrate and nitrite ions, for which food and water are the major pathways of human exposure. The nitrate and nitrite salts described in Section 1.1 represent some of the potential anthropogenic sources of these compounds in food and water, and their use is presented in relation to exposure by ingestion; however, it is not the intention of this monograph to evaluate the carcinogenicity of any of the individual salts. The highly water-soluble nitrate and nitrite ions are of interest here and the patterns of occurrence and levels of human exposures to nitrate and nitrite ions are described in Sections 1.3 and 1.4. 1. Exposure Data Nitrate and nitrite are naturally occurring ions that are part of the nitrogen cycle and are ubiquitous in the environment. Both are products of the oxidation of nitrogen (which comprises approximately 78% of the earth’s atmosphere) by microorganisms in plants, soil or water. Nitrate is the more stable form of oxidized nitrogen but can be reduced by microbial action to nitrite, which is moderately chemically reactive. Chemical and biological processes can further reduce nitrite to various compounds or oxidize it to nitrate. Nitrate salts are used widely as inorganic fertilizers, and are also used in explosives, as oxidizing agents in the chemical industry and as food preservatives. Nitrite salts have been also used as food preservatives, especially to cure meats (Environmental Protection Agency, 1987; Health Canada, 1992; Pokorny et al. , 2006). During the second half of the twentieth century, production of nitrogen compounds by humans increased dramatically—intentionally through the use of fertilizers or unintentionally as a by-product of the combustion of fossil fuels. In fact, it has been reported that, since the end of the twentieth century, humans have been adding more nitrogen compounds to the nitrogen cycle than all other sources combined (Fields, 2004). –45– 46 IARC MONOGRAPHS VOLUME 94 1.1 Chemical and physical data 1.1.1 Nomenclature, molecular formulae, relative molecular masses and chemical and physical properties From Chapman and Hall/CRC (2006) and Toxnet (2006), unless otherwise indicated Nitrate ion Chem. Abstr. Serv. (CAS) Reg. No. : 14797-55-8 Deleted CAS Reg. Nos : 23746-18-1; 34236-35-6; 73394-83-9 Chem. Abstr. Name : Nitrate IUPAC Systematic Name : Nitrate − − Synonyms : Nitrate (NO 3 ); nitrate(1 −); nitrate ion; nitrate ion (NO 3 ); nitrate ion(1 −); nitrato; nitric acid, ion(1 −) O ONO – NO 3 Relative molecular mass: 62.005 (a) Acid : Conjugated base of the strong acid HNO 3; p Ka = –1.3 (WHO, 2003a) (b) Reactivity : Unreactive (WHO, 2003a) Nitrite ion Chem. Abstr. Serv. Reg. No. : 14797-65-0 Deleted CAS Reg. Nos : 12183-96-9; 114466-53-4 Chem. Abstr. Name : Nitrite IUPAC Systematic Name : Nitrite − − Synonyms : Nitrite (NO 2 ); nitrite(1 −); nitrite anion; nitrite ion; nitrite ion (NO 2 ); nitrite ion(1 −); nitrogen dioxide(1 −); nitrogen dioxide ion(1 −); nitrogen peroxide ion(1 −); nitrous acid, ion(1 −) ONO – NO 2 Relative molecular mass: 45.995 (a) Acid : Conjugated base of the weak acid HNO 2; pKa = 3.4 (WHO, 2003a) (b) Reactivity : Reactive; oxidizes antioxidants, the divalent iron (Fe 2+ ) of haemoglobin to trivalent iron (Fe 3+ ) and primary amines; nitrosates several amines and amides (WHO, 2003a). Ammonium nitrate Chem. Abstr. Serv. Reg . No.: 6484-52-2 INGESTED NITRATE AND NITRITE 47 Deleted CAS Reg. No. : 95255-40-6 Chem. Abstr. Name : Nitric acid, ammonium salt IUPAC Systematic Name : Nitric acid, ammonium salt Synonyms : Ammonium nitrate; ammonium nitrate (NH 4NO 3); Emulite; EXP 200; German saltpeter; Norge salpeter; Norway salpeter; Norwegian salpeter; Plenco 12203; Varioform I; ZhVK O ONO NH4 NH 4NO 3 Relative molecular mass: 80.043 (a) Description : White hygroscopic crystals; exists in five crystalline forms (b) Boiling-point : Decomposes at about 210 °C, mostly into water and nitrous oxide (Merck & Co., 2005) (c) Melting-point : 169.7 °C (Lide, 2005) (d) Density : 1.725 g/cm 3 (e) Solubility : Very soluble in water (118.3 g/100 g at 0 °C; 213 g/100 g at 25 °C; 871 g/100 g at 100 °C) (Lide, 2005); soluble in acetone, ammonia, ethanol (3.8 g/100 g at 20 °C), isopropanol and methanol (17.1 g/100 g at 20 °C); insoluble in diethyl ether (Merck & Co., 2005) (f) pH : 0.1 M solution in water is 5.43. Sodium nitrate Chem. Abstr. Serv. Reg. No. : 7631-99-4 Deleted CAS Reg. No. : 862599-22-2 Chem. Abstr. Name : Nitric acid, sodium salt IUPAC Systematic Name : Nitric acid, sodium salt Synonyms : Chile salpeter; niter; nitric acid sodium salt (1:1); salpeter; soda niter O ONO Na NaNO 3 Relative molecular mass: 84.995 (a) Description : Colourless trigonal (rhombohedral) crystals; undergoes transition to high-temperature polymorph at ~278 °C (b) Boiling-point : 380 °C; decomposes on heating to form sodium nitrite (Weast, 1979). (c) Melting-point : 306 °C (d) Density : 2.26 g/cm 3 (Merck & Co., 2005) 48 IARC MONOGRAPHS VOLUME 94 (e) Solubility : Very soluble in water (92 g/100 g at 25 °C; 180 g/100 g at 100 °C); very soluble in ammonia; soluble in ethanol and methanol; very slightly soluble in acetone and glycerol; practically insoluble in dimethyl ether (Weast, 1979) (f) pH : An aqueous solution is neutral (Merck & Co., 2005). Sodium nitrite Chem. Abstr. Serv. Reg. No. : 7632-00-0 Deleted CAS Reg. Nos: 32863-15-3; 56227-20-4; 82497-43-6; 82998-40-1 Chem. Abstr. Name : Nitrous acid, sodium salt IUPAC Systematic Name : Nitrous acid, sodium salt Synonyms : Nitrous acid soda; nitrous acid sodium salt (1:1) ONO Na NaNO 2 Relative molecular mass: 68.985 (a) Description : White to pale yellow, hygroscopic, orthorhombic crystals (Lide, 2005) (b) Boiling-point : > 320 °C (decomposes) (Lide, 2005); undergoes transition to high- temperature orthorhombic polymorph at 158 °C. (c) Melting-point : 271 °C (d) Density : 2.17 g/cm 3 (Merck & Co., 2005) (e) Solubility : Very soluble in water (84.8 g/100 g at 25 °C); very soluble in ammonia; slightly soluble in ethanol (3 g/100 g at 20 °C) (Lide, 2005) and methanol (4.4 g/100 g at 20 °C); sparingly soluble in diethyl ether (0.3 g/100 g at 20 °C) (Weast, 1989) (f) pH : An aqueous solution is alkaline (~9) (Merck & Co., 2005). Potassium nitrate Chem. Abstr. Serv. Reg. No .: 7757-79-1 Deleted CAS Reg. No .: 96193-83-8 Chem. Abstr. Name : Nitric acid, potassium salt IUPAC Systematic Name : Nitric acid, potassium salt Synonyms : Niter; nitre; nitric acid potassium salt (1:1); salpeter O ONO K KNO 3 Relative molecular mass: 101.103 (a) Description : Colourless, orthorhombic crystals INGESTED NITRATE AND NITRITE 49 (b) Boiling-point : 400 °C (decomposes) (Lide, 2005); undergoes orthorhombic to rhombohedral form transition at 128 °C; cooling the rhombohedral form gives a metastable rhombohedral polymorph that exists between 128 °C and 109 °C. (c) Melting-point : 334 °C (d) Density : 2.11 g/cm 3 (Merck & Co., 2005) (e) Solubility : Very soluble in water (13 g/100 g at 0 °C; 38.3 g/100 g at 25 °C; 247 g/100 g at 100 °C); soluble in ammonia; insoluble in diethyl ether and ethanol (Weast, 1989; Lide, 2005) (f) pH : ~7 (Merck & Co., 2005) Potassium nitrite Chem. Abstr. Serv. Reg. No. : 7758-09-0 Chem. Abstr. Name : Nitrous acid, potassium salt IUPAC Systematic Name : Nitrous acid, potassium salt Synonyms : Chile salpeter; niter; nitric acid sodium salt (1:1); salpeter; soda niter ONO K KNO 2 Relative molecular mass: 85.093 (a) Description : Pale yellow, hexagonal crystals; white, hygroscopic crystals (Lide, 2005) (b) Boiling-point : 537 °C (explodes) (Lide, 2005); undergoes transition from rhombohedral to cubic form at 70 °C; disproportionates on heating in the absence of air to form potassium nitrate (KNO 3), potassium oxide (K 2O) and evolving nitrogen. (c) Melting-point : 440 °C (d) Density : 1.915 g/cm 3 (Lide, 2005) (e) Solubility : Very soluble in water (281 g/100 g at 0 °C; 312 g/100 g at 25 °C; 413 g/100 g at 100 °C); very soluble in ammonia; slightly soluble in ethanol (Weast, 1989; Lide, 2005) 1.1.2 Physicochemical properties Concentrations of nitrate and nitrite can be expressed in different units, as either milligrams per litre (mg/L), milligrams of nitrate nitrogen per litre (mg/L nitrate-N) or milligrams of nitrite nitrogen per litre (mg/L nitrite-N). It can also be expressed in terms of moles (or millimoles); the latter simplifies the comparison of nitrate and nitrite with regard to exposure and their relative contributions to N-nitroso compounds. Conversion factors between the different units are given in Table 1.1 (Environmental Protection Agency, 1987; WHO, 2003a). 50 IARC MONOGRAPHS VOLUME 94 Table 1.1. Conversion factors between different units – – – – mM mg/L NO 3 mg/L NO 3 -N mg/L NO 2 mg/L NO 2 -N mM 1 62 14 46 14 – mg/L NO 3 0.016 1 0.226 – – – mg/L NO 3 -N 0.0714 4.429 1 – – – mg/L NO 2 0.0217 – – 1 0.304 – mg/L NO 2 -N 0.0714 – – 3.29 1 From Environmental Protection Agency (1987); WHO (2003a) – – – – NO 3 , nitrate; NO 3 -N, nitrate nitrogen; NO 2 , nitrite; NO 2 -N, nitrite nitrogen 1.2 Analysis Spectrometric techniques are used for the determination of nitrate in water. Selected methods for the determination of nitrates and nitrites in various matrices are presented in Table 1.2. A molecular absorption spectrometric method is available for the determination of nitrite in drinking-water, raw water and wastewater (International Standards Organization, 1984b).
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