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Sulfurous Acid Sulfurous Acid Crops 1 2 Identification of Petitioned Substance 3 4 Chemical Names: 16 Trade Names: 5 sulfurous acid 17 None Listed 6 hydrogen sulfite 18 7 CAS Numbers: 8 Other Names: 7782-99-2 9 sulphurous acid 10 sulfur dioxide solution Other Codes: 11 schweflige saure CHEBI 48854 12 acide sulfureux EINECS 231-973-1 13 acido sulfuroso UN 1833 14 InChlKey LSNNMFCWUKXFEE-UHFFAOYSA-N 15 19 20 Summary of Petitioned Use 21 22 Following a petition submitted in 2008, the NOSB recommended the adoption of sulfurous acid, as a soil 23 amendment in a May 6, 2009 vote (NOSB, 2009 a, b, c, d). A proposed rule was published on January 10, 24 2010 (Pegg, 2010). The final rule was published on July 6, 2010. Sulfurous acid was added to the National 25 List (Electronic Code of Federal Regulations, 2013) as follows: 26 § 205.601 Synthetic substances allowed for use in organic crop production, (j) as plant or soil 27 amendments, (9) sulfurous acid (CAS #7782-99-2) for on-farm generation of substance utilizing 28 99% purity elemental sulfur per paragraph (j)(2) of this section. 29 As required by the Organic Foods Production Act, the National Organic Standards Board has the 30 responsibility to review each substance on the National List within five years of its adoption to determine 31 whether the substance should be renewed or removed from the National List. The NOSB has requested 32 an updated technical evaluation report for sulfurous acid to support their decision-making. 33 The current listing for sulfurous acid is scheduled to sunset on 7/7/2015. 34 35 Characterization of Petitioned Substance 36 37 Composition of the Substance: 38 39 Sulfurous acid is the name given to water that has been sprayed through smoke and fumes produced by 40 burning elemental sulfur. The composition of this fluid is complex containing a number of dissolved 41 substances including but not limited to sulfur dioxide, hydrogen sulfide and hydrogen sulfite (bisulfite). 42 Because sulfur dioxide forms hydrogen sulfite when dissolved in aqueous solution and hydrogen sulfite 43 is acidic, effluent water from the sulfurous acid generator becomes acidified. Acidified irrigation water is 44 used to adjust soil pH into the acidic range. 45 46 Source or Origin of the Substance: 47 48 The primary ingredients used in the preparation of sulfurous acid are water and elemental sulfur. 49 Elemental sulfur was once mined and extracted from salt domes where it sometimes occurs in nearly 50 pure form, but this method has been obsolete since the late 20th century. Today, almost all elemental 51 sulfur is produced as a byproduct of coal, natural gas and petroleum refinement (Davis and Detro, 1992). 52 Desulfurization of diesel fuel, gasoline, and jet fuel to meet today’s air pollution standards requires the ___________________________________ January 30, 2014 Technical Evaluation Report Page 1 of 11 Compiled by the USDA AMS Agricultural Analytics Division for the USDA National Organic Program Technical Evaluation Report Sulfurous Acid Crops 53 reduction of sulfur concentration from levels exceeding 500 ppm to less than 15 ppm (Song, 2003). 54 Residual sulfur is removed from petroleum, natural gas and coal by the Claus process and refined to very 55 high levels of purity suitable for sulfurous acid production (El-Bishtawi and Haimour, 2004; Elsner et al., 56 2003). 57 58 Properties of the Substance: 59 60 Sulfurous acid is produced by dissolving the fumes of burning sulfur in irrigation water. Sulfur is an 61 odorless, tasteless, light yellow solid usually sold in blocks or pellets. It is easily crushed into a powder. 62 Sulfur is a reactive element that given favorable circumstances combines with all other elements except 63 gases, gold, and platinum (Georgia Gulf Sulfur Corporation, 2000). Burning sulfur emits sulfur dioxide. 64 Sulfur dioxide dissolved in aqueous solution is called sulfurous acid. In fact, sulfurous acid is not 65 chemically stable at temperatures above -196.15 o C. The predominate form that sulfur dioxide take in − 66 solution is as hydrogen sulfite (bisulfite, HSO3 ―Equation 1). Hydrogen sulfite is acidic in aqueous 67 solution (pKa=6.97). Molten sulfur can also evolve hydrogen sulfide. The basic physical properties for 68 sulfur are boiling point: 832 o F (445 o C); melting point: 230 to 246 o F (113 to 120 o C); vapor pressure: o 69 4x10-6 mm Hg @ 86 of (30 C); specific gravity (H2O = 1): approx. 1.96 (varies); percent volatiles: 70 negligible; Flashpoint: 405oF (207.2oC), Flammability Limits: Lower explosive limit: 3.3% Upper explosive 71 limit: 46.0%, Auto-ignition Temperature: 478-511oF (248-266oC) and solubility: insoluble in water. Sulfur 72 dioxide (CAS 7446-09-5), a product of burning sulfur and the active ingredient of sulfurous acid, is a toxic 73 gas with a pungent irritating smell. Sulfur dioxide forms hydrogen sulfite when combined with water. 74 Hydrogen sulfite is a weak acid. 75 − + Equation 1 SO2 + H2O ⇌ HSO3 + H 76 77 Specific Uses of the Substance: 78 79 Sulfurous acid is useful in arid and semi-arid agricultural regions where irrigation water and soil are 80 likely to be saline and alkaline (Allison et al., 1954; FAO, 1990). The product is used to improve water 81 quality by instantly reducing pH. In some climates and topographies, decreased soil moisture results in 82 accumulation of soluble salts and alkali carbonates with replacement of calcium and magnesium by 83 sodium in the adsorbing complex of soil. Humus, an important part of this complex is also gradually 84 reduced and replaced by alumino-silicate clay and a shallow potentially precipitated humus layer 85 saturated with sodium (Wakman, 1936). Sulfurous acid reduces soil pH and changes mineral solubility. 86 This results in a short term improvement of the humus layer and a better yield for some crops. In 87 reducing alkalinity, sulfurous acid temporarily removes incrustations from roots, releases mineral plant 88 food, disintegrates hardpan, helps to breakdown organic matter and increases nitrates (Pacific Coast 89 Nurseryman, 1945). In contrast, a related product, elemental sulfur, is commonly used for the same 90 purpose. Although longer lasting, it requires months or years to be effective. The addition of sulfite to 91 water and soil by sulfurous acid provides a substrate for sulfur-bacteria that in turn provides available 92 and organic sulfur. 93 94 Approved Legal Uses of the Substance: 95 96 The SO2 generator developed by Harmon Systems International, LLC can be used to treat coal bed 97 methane production (CBM) water (EPA, 2004). In 2004, US Environmental Protection Agency (EPA) 98 concluded that it should not identify the CBM industry for effluent guidelines rulemaking. 99 A proposal to revoke the EPA exemption from a tolerance requirement for sulfurous acid use as a 100 pesticide was filed on June 1, 2005 (EPA, 2005). Subsequently, sulfurous acid was removed from EPA’s 101 list of registered pesticides; its list of inert ingredients for food use pre- and post-harvest, exemptions 102 from the requirements for a tolerance (40 CFR 180.910), and its list of chemicals not requiring a tolerance 103 or an exemption from tolerance in food (40 CFR 180). 1/30/14 Compiled by USDA AMS Agricultural Analytics Division for the USDA National Organic Program Page 2 of 11 Technical Evaluation Report Sulfurous Acid Crops 104 Sulfurous acid is currently listed by the EPA as an inert ingredient permitted for use in nonfood use 105 pesticide products (EPA, 2011). An inert ingredient is any substance other than an “active” ingredient, 106 which is intentionally included in a pesticide product. It is important to note, the term “inert” does not 107 imply that the chemical is nontoxic. All inert ingredients in pesticide products, including those in an inert 108 mixture, must be approved for use by the EPA. A tolerance or tolerance exemption is required only for 109 those inert ingredients applied to food. Impurities are not included in the definition of inert ingredient. 110 Sulfur dioxide, the active ingredient of sulfurous acid, is a major contributor to air pollution attributed to 111 burning fossil fuel. As a result, EPA includes sulfur dioxide in many documents pertaining to sulfur 112 recovery, fossil fuel refinement and air pollution abatement. Despite the withdrawn tolerance exemption, 113 EPA has not established a tolerance for sulfurous acid effluent produced by a sulfurous acid generator. 114 However, a tolerance of 10 ppm has been set for the use of sulfur dioxide as a fungicide and a food 115 preservative. 116 The US Food and Drug Administration finds sulfur dioxide generally recognized as safe when used in 117 accordance with good manufacturing practice, except that it is not used in meats; in food recognized as a 118 source of vitamin B1; on fruits or vegetables intended to be served raw to consumers or sold raw to 119 consumers, or to be presented to consumers as fresh (FDA, 2013a). Food grade sulfurous acid may be 120 employed to assist caramelization in food, in amounts consistent with good manufacturing practice (EPA, 121 2013b). 122 The USDA includes sulfurous acid in the National Organic Program’s National List for use in crop 123 production as a soil amendment when 99% pure elemental sulfur is used (USDA, 2010). 124 125 Action of the Substance: 126 127 Saline and alkali soil conditions reduce the value and productivity of considerable areas of land. The 128 problem is an ancient one, and there is much information on this subject in technical literature (Cowen, 129 1999). For many farms in dry climates, rain is sporadic and the only naturally available water source is 130 alkaline or saline, moreover these farms may be using irrigation systems where the water source contains 131 a high level of dissolved mineral salts.
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