UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, D.C. 20460

July 29, 2014



### MEMORANDUM OFFICE OF CHEMICAL SAFETY AND POLLUTION PREVENTION



### SUBJECT: PC Code: 878001; Sulfuric Acid; Human Health Risk Assessment and Ecological Effects Assessment to Support Proposed Exemption from the Requirement ofa Tolerance When Used as Inert Ingredients in Pest icide Formulations.



### A

ll PC Code: 878001 

### DP Barcode: N/A 

### Decision No.: N/ A

Petition No: IN-10654

Inert Tracking No: N/A Regulatory Action : Inert Tolerance Exemption; 40 CFR 1 80.940(a)

. 

### All CAS Reg

. No : 7664- 93-9



### FROM: Lisa Austin, Ph.D., Toxicologist

# ~**~** Inert Ingredient Assessment Branch (IIAB) Registration Division (7505P)


### THROUGH: Kerry Leifer, Team Leader Inert Ingredient Assessment Branch (IIA Registration Division (7505P)


### TO: PV Shah, Ph.D., Branch Chief Inert Ingredient Assessment Branch (IIAB) Registration Division (7505P)

Page 1 of 13

### I. EXECUTIVE SUMMARY

EPA received a petition (IN-10654) from Exponent, Inc. (1150 Connecticut Avenue, NW Washington, DC 20036), on behalfofEcolab (370 N. Wabasha St., St. Paul, MN 55102) requesting an exemption from the requirement ofa tolerance for sulfuric acid (CAS Reg. No

. 7664-93-9) for use as an inert ingredient on food contact surfaces in public eating places, dairy processing equipment and food processing equipment and utensils up to 600 ppm in microbial formulations under 40 CFR part 180.940(a). EPA published the notice of filing (NOF) for this petition in the Federal Register on July 19, 2013 (78 FR 43117). No comments were received in response to this notice. Currently, sulfuric acid is exempt from the requirements ofa tolerance under 40 CFR § 180.940(b) and (c) (dairy processing equipment and food processing equipment and utensils; limited to 288 and 228 ppm, respectively), 40 CFR § 180.910 (pre- and post-harvest crop uses as pH control agent, limited to 10% in pesticide formulations) and 40 CFR § 180.1019 (limited to 10% in pesticide formulations). It is approved by the Food and Drug Administration under 21 CFR § 184.1095 for Direct Food Substances Affirmed as Generally Recognized as Safe (GRAS).
In September, 2006, the EPA published the "Tolerance Reassessmen t Decisions for 40 CFR §180.940 Tolerance Exemptions" which included sulfuric acid. In 2008, the Agency published the "Mineral Acids Summary document: Registration Review", "Sulfuric acid on potato vines: Registration Review Scoping Document for Human Health Assessments", "Summary ofHuman Health Effects Data for the Mineral Acids Registration Review Decision Document" and the "Summary ofProduct Chemistry Fate, and Ecotoxicology Data for the Sulfuric Acid Registration Review Decision Document". The toxicological database for sulfuric acid is considered adequate. The conclusions and recommendations presented herein rely principally on the Agency's previous analyses. No new data have been received by the Agency which might alter the conclusions presented in the 2008 Mineral Acids Registration Review Decision Document.
Sulfuric acid is a strong acid. In water it dissociates into sulfate ions and hydrogen protons, it also decreases the pH. The extent and duration ofthe drop will depend on the neutralizing ions, the buffering capacity, and the dilution. Many ofthe end-use products are significantly diluted and this has a large effect on the overall toxicity ofthe chemical as the acid is neutralized in water and would dissociate to ions. (EPA, November 25, 2008).
As no new data were submitted for review, the following summary was reproduced from the Registrant's submission which included the following documents: the EPA's "Tolerance Reassessment Decision for 40 CFR 

### § 180.940 Tolerance Exemptions", "Summary ofProduct Chemistry Fate, and Ecotoxicology Data for the Sulfuric Acid Registration Review Decision Document", "Sulfuric acid on potato vines: Registration Review Scoping Document for Human Health Assessments", and "Summary ofHuman Health Effects Data for the Mineral Acids Registration Review Decision Document". Also, included in the submission was the "Sulfuric Acid SIDS Initial Assessment Report for 11th SIAM UNEP Publication", this was also reproduced.

Page 2 of13The acute oral toxicity ofsulfuric acid in rats is moderate, the LDSO =350 mg/kg (toxicity category II). The acute dermal toxicity in rabbits is moderate, the LD 50> 2000 mg/kg (toxicity category III)

. The acute inhalation in guinea pigs is in toxicity category III, the LCSO is 18 mg/m3. Sulfuric acid is corrosive to the eyes and skin in rabbits.
Data from repeated dosing toxicity studies with animals are not available for sulfuric acid. Based on the toxicity data reviewed for the 2002 TRED, there are no adverse effects that would be expected from dietary exposure to the general population or infants and children for sulfuric acid. In fact, sulfuric acid would not be present in consumed foods. The small amounts ofacids that might be added to a food during processing react rapidly with a food substance. Thus, the exposure is actually to sulfate residues. In an aqueous environment, sulfuric acid rapidly ionizes to sulfate ions and enters the body electrolyte pool (OECD SIDS, Sulfuric Acid, 2001). Following ingestion, sulfate anions are predominantly not absorbed from the gastrointestinal tract and are excreted unchanged in urine. However, the sulfate anion is a normal constituent in the body, predominantly resulting from the body's metabolism ofsulfur-containing food sources such as foods containing t he essential amino acids cysteine and methionine. Sulfate anions are vital componen ts in a number ofhuman biosynthetic pathways such as cartilage production and the formation of pancreatic digestive enzymes
. Additionally, the sulfate anion is also an important conjugate in the Phase II conjugation/ elimination ofoxidized (OH) aromatic ring metabolites and for hydroxyl steroid hormones, such as estrogen, where it acts as a transport agent to target organ tissue receptors. Therefore, the sulfate anion will not pla y a specific toxicological role.
Sulfuric acid was not mutagenic in the Ames test. It caused chromosomal aberrations in a nonbacterial test 

### in vitro

. However, it is well known that the aberrations were a consequence of reduced pH.
Neither a neurotoxicity nor an immunotoxicity study was avail(:lble for review. However, any sulfuric acid absorbed into the body would be in the form of inorganic sulfate, which is indistinguishable from endogenous sulfate. As a normal body constituent, sulfate is unlikely to be neurotoxic or immunotoxic

. Dietary exposure (food and drinking water) to sulfuric acid can occur following ingestion offoods with residues from food-contact surface sanitizing solutions for public eating places, treated dairyand food-processing equipment and utensils; pre- and post-harvest crop uses and as a direct food additives. However, a quantitative dietary exposure assessment was not conducted since an endpoint for risk assessment was not identified.
Residential (dermal and inhalation) exposure are not expected from the current requested use pattern. However, residential (dermal and inhalation) exposure can occur from the use of consumer products containing sulfuric acid (ie. stain remover, drain solutions). Since an endpoint for ri sk assessment was not identified, a quantitative residential exposure assessment for sulfuric acid was not conducted.
In considering aggregate exposure, information concerning exposures from the pesticide residue in food due to the use ofsulfuric acid on pre- or post-harvest commodities; dairy processing equipment, food processing equipment and utensils, a direct food substance; and all other nonoccupational exposures, including drinking water from ground water or surface water and exposure Page 3 of13through pesticide use in gardens, lawns, or buildings (residential and other indoor uses). Since a quantitative assessment was not performed an aggregate assessment was not necessary.
The Agency believes that amending the existing tolerance exemption to include 40 CFR 

### § 180.940(a) will not significantly increase occupational

.exposure. The change in use pattern would be expanded to include food contact surfaces such as tableware, utensils, dairies and beverage and food processing plants. Based on the regulatory history of sulfuric acid and no new toxicological information to indicate otherwise, it is not necessary to quantitatively assess occupational exposure.
Potential areas of environmentaljustice concerns, to the extent possible, were considered in this human health risk assessment, in accordance with U.W. Executive Order 12898 "Federa l Actions to Address Environmental Justice in Minority Populations and Low-Income Populations" http ://www.eh. doe.gov /oepalguidance/justice /eo 12898.pdf.
Environmental fate data for sulfuric acid were not submitted for review. All environmental fate and ecological effects data for sulfuric acid were waived. The Agency concluded that the registered uses ofsulfuric acid did not pose unreasonable adverse effects and risks to the environment (Gowda, S. 11124 /2008, D359048). Taking into consideration all available information on sulfuric acid (CAS Reg. No. 7664-93-9), EPA concludes that there is a reasonable certainty that no harm will result to the general population or to infants and children from exposure to sulfuric acid. Theref ore, the establishment ofan exemption from tolerance under 40 CFR 180.940(a) for residues of sulfuric acid for use as an inert ingredient on food contact surfaces in public eating places, dairy processing equipment and food processing equipment and utensil s up to 600 ppm in microbial formulations in the endproduct formulation can be considered safe under section 408 ofthe FFDCA. 

### II. BACKGROUND

On September 30, 20 13 Exponent, Inc. (1150 Connecticut Avenue, NW Washington, DC 20036 submitted a petition (IN-1 0654) requesting an amendment to 40 CFR 180 by establishing an exemption from the requirement ofa tolerance for residues of sulfuric acid (CAS Reg. No. 7664- 93-9), when used as an inert ingredient, at a concentration not to exceed 600 ppm in microbial formulations used on food contact surfaces in public eating places, dairy processing equipment and food processing equipment and utensils. EPA published the NOF for this petition in the Federal Register on February 25, 2014 (79 FR 10460). No comments were received in response to this notice.
Sulfuric acid is a clear, colorless, odorless, viscous liquid that is very corrosive and infinitely soluble in water in all proportions. It is used in many industries, as agricultural fertilizer, production ofdyes, alcohols, plastics, rubber, ether, glue, film , explosives, drugs, paints, food containers , wood preservatives, soaps and detergents , pharmaceutical products, petroleum products, pulp and paper. Principal uses include ore processing, fertilizer manufacturing, oil refining, wastewater processing, and chemical synthesis.

Page 4 of 13Currently, sulfuric acid is exempt from the requirements ofa tolerance under 40 CFR 

### § 180.940(b) and 40 CFR 

### § 180.940( c) when used in antimicrobial pesticide formulations for uses on dairy processing equipment and food processing equipment and utensil, when end-use concentrations do not exceed 288 and 228 ppm, respectively, when ready for use. It is also approved under 40 CFR 

### §180.910 for pre- and post-harvest crop uses or raw agricultural commodities after harvest at up to 1

0% in a pesticide formulation. It is approved as an active ingredient and has an exemption from the requirement ofa tolerance as listed in 40 CFR 

### § 180.1019 with a limitation of 10% ofthe pesticide formulation (non-aerosol formulations only).
In addition, it is approved by the Food and Drug Administration under 21 CFR 

### § 184.1095 (pH control agent, processing aid) for Direct Food Substances Affirmed as Generally Recognized as Safe (GRAS). Previously, sulfuric acid was included in the Mineral Acids Registrat ion Eligibility Document published in December, 1993. Its inert and active ingredient uses were reassessed in 2006. In 2008 , the Registration Review docket for Mineral Acids (including sulfuric acid) was opened and the following documents were included: Summary ofHuman Health Effects Data for the Mineral Acids Registration Review Decision Document", the " Summary ofProduct Chemistry Fate, and Ecotoxicology Data for the Sulfuric Acid Registration Review Decision Document" , Mineral Acids Summary Document: Registration Review", and " Sulfuric acid on potato vines: Registration Review Scoping Docu ment for Human Health Assessments". The toxicological database for sulfuric acid is adequate.
Much ofthe discussion ofsulfuric acid is taken from the Registrant' s petition which includes the aforementioned documents.


### III. PHYSICAL/CHEMICAL PROPERTIES

Sulfuric acid is a clear, colorless, odorless, viscous liquid that is very corrosive and infinitely soluble in water in all proportions. In water sulfuric acid completely dissociates to hydronium cations (H30+ ) and sulfate anions (Soi·).

Table 1. Physical and Chemical Properties of Sulfuric Acid

Parameter Value Source

0 II so-s- oa Structure II Summary ofProduct Chemistry, 0 Environmental Fate and Ecotoxicity Data for the Sulfuric Acid Registration Revi ew Chemical Name Oil ofvitriol, Dihydrogen sulfate Decision Document CAS# 7664-93-9 Molecular Weight (g/mol) 98.078 Common Names Sulfuric acid
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