NITROCELLULOSE Health Advisory Office of Drinking Water U.S. Environmental Protection Agency Washington, DC 20460 ------- PREFACE This report was prepared in accordance vich che Memorandum of Understa-dirg becveen che Department of che Army, Deputy for Environment, Safety and Occupational Healch (OASAd&L)) and the U.S. Environmental Protection Agency (EPA), Office of Drinking Water (ODW), Criteria and Standards Division, for the purpose of developing drinking water Health Advisories (HAs) for selected environmental contaminants, as requested by the Army. Health Advisories provide specific advice on the levels of contaminancs in drinking water at which adverse health effects would not be anticipated and which include a margin of safety so as to protect the mosc sensitive member of the population at risk. A Health Advisory provides health effects guidelines and analytical methods and recommends treatment techniques on a case-by-case basis. These advisories are normally prepared for One-day, 10-day, Longer-term and Lifetime exposure periods where available toxlcological data permit. These advisories do not condone the presence of contaminants in drinking water; nor are they legally enforceable standards. They are not Issued as official regulations, and they may or may not lead to the Issuance of national standards or Maximum Contaminant Levels (MCLs). This report Is the produce of the foregoing process. Available toxlcological data, as provided by the Army, on the munitions chemical, nitrocellulose (NC), have been reviewed, and the relevane findings are presented In this report in a manner so as to allow for an evaluation of the data without continued reference to che primary documents. Significant chemical and physical properties of NC as well as potential sources of exposure are provided as a means of identifying the subject chemical. Data on the pharmacokinetic properties, although somewhat limited in scope, are summarized. All available toxlcological data, including short-term, longer-term and lifetime feeding studies in three species* as well as the results of reproductive and genetic toxicology studies, have been reviewed, and those effects deemed relevant to Che ingestion of NC are suaaarlzed. Results of Immunologic and carcinogenic studies ars also Included. This roport also includes a section describing state-of-the-art methods of analyses foe BC In drinking water and Includes essential treatment techniques appropriate for NC removal froa an affected water supply, should the levels of NC in the drinking water reach a level considered unpalatable due to taste, clarity or similar indicators. This report has been submitted to a critical review by the EPA to include a panel of Health Effects Branch (HEB) toxlcologlsts. Their comments, as appropriate, have been Incorporated Into this report. A companion document, "Data Deficiencies/Problem Areas and Recommendations ------- for Additional Data Base Development for Nitrocellulose" ls included in ;-13 report under Appendix 2. I would like to express ny thanks to Dr. John Glennon, Life Systems, Inc., who afforded valuable coordination and logistical assistance. I also thank Dr. Janet Normandy, Ms. Lori Gordon and Dr. William Hartley who provided the extensive technical skills required for the preparation of this report. I am grateful to the following members of the EPA Tox-Review Panel, Dr. Kenneth Bailey, Dr. Aablka Bathija, Dr. Bill Marcus and Mr. Bruce Mintz, who took time to review this report and Co provide their invaluable input. Finally, I would like to thank Dr. Edward Ohanlan, Chief, Health Effects Branch, Dr. Joseph Cotruvo, Director Criteria and Standards Division, and Dr. Penelope Fenner-Crlsp, Manager, Health Advisory Program, for providing me vich the opportunity and encouragement to be a part of this project. The preparation of this Advisory was funded in part by Interagency Agreement (IAG) 85PP5869 between the U.S. EPA and the U.S. Army Medical Research and Development Command (USAMKDC). This IAG was conducted with the technical support of the U.S. Army Biomedical Research and Development Laboratory (USABRDL). Krishan Khanna, Project Officer Office of Drinking Water ------- TA3L- Of CONTENTS °3Ee I. INTRODUCTION I-1 II. GENERAL INFORMATION II-l III. SOURCES OF EXPOSURE Ill-1 IV. PHARMACOKINETICS IV-1 V. HEALTH EFFECTS v-l A. Short-Term Exposure ' V-l 1. Primary Skin and Eye Irritation V-l B. Longer-Term Exposure V-l 1. Thirteen-Week Studies V-l 2. Lifetime Exposure V-3 C. Genetic Toxicology V-7 D. Carcinogenicity V-8 E. Reproductive Effects V-9 F. Teratogenicity . . V-10 G. Immunologic Effects V-10 VI. HEALTH ADVISORY DEVELOPMENT VI-1 VII. ANALYSIS VII-l VIII. TREATMENT VIII-1 IX. CONCLUSIONS AND RECOMMENDATIONS IX-1 X. REFERENCES ' X-l LIST OF TABLES Table Il-i General Chemical and Physical Properties of Cellulose II-2 Trinitrate ------- APPENDiC-S Appendix A1 Calculation Mechods AL-l A2 Daca Deficiencies/Problem Areas and Recommendations for Additional Data Base Development for Nitrocellulose a2-1 ------- I. INTRODUCTION Th« Health Advisory (HA) Program, sponsored by the Office of Drir.kir.g Water (ODW), provides information on the health effects, analytical methodology and treatment technology that would be useful in dealing vie11 che contamination of.drinking water. Health Advisories describe nonregulatorv concentrations of drinking water contaminants at which adverse health effects would not b« anticipated to occur over specific exposure durations. Health Advisories contain a margin of safety to protect sensitive members of the population. Health Advisories serve as Informal technical guidance to assist Federal, State and local officials responsible for protecting public health when emergency spills or contamination situations occur. They are not to be construed as legally enforceable Federal standards. The Advisories are subject to change as new information becomes available. Health Advisories are developed for One-day, Ten-day. Longer-term (approximately 7 years, or 10Z of an individual's lifetime) apd Lifetime exposures based on data describing noncarcinogenlc end points of toxicity. Health Advisories do not quantitatively incorporate any potential carcinogenic risk from such exposure. For those substances that are known or probable human carcinogens, according to the Agency classification scheme (Croup A or B), Lifetime HAs are not recommended. The chemical concentration values for Croup A or B carelnogens are correlated with carcinogenic risk estimates by employing a cancer potency (unle risk) value together vlth assumptions for lifetime exposure and the consumption of drinking water. The cancer unit risk is usually derived from the linear multistage model with 95 J upper confidence limits. This provides a low-dose estimate of cancer risk to humans that is considered unlikely to pose a carcinogenic risk In excess of the stated values. Excess cancer risk estimates may also be calculated using the One-hit, Weibull, Logic and Problt models. There is no current understanding of the biological mechanisms involved in cancer to suggest that any one of these models is able to predict risk more accurately than another. Because e.ach model la based upon differing assumptions^ the estimates that are derived can differ by several orders of magnitude. I-i ------- CZSI3AL INFORMATION As described by Sullivan ec al. (1978), nitrocellulose, or cellulose trinitrate. is a non-volatile, fibrous, cotton-like, white solid (specific graviv 1.66) consisting of chains of beta, 1 co 4 linked glucoside units in which the hydroxy1 groups of the glucose subunits have reacted to form nitrate esters. The chemical formula is approximately (ONO^) ^ lfl» c^e °olecular weight depends on chain length, and the degree of polymerization (DP) varies appreciably. Cotton lmters and wood pulp used for the preparation of military grades of NC have a DP of approximately 1,000 to 1,500. The fully nitrated form of NC has a nitrogen concent of 14.14Z and a formula weight of 297.14. This degree of nitration is difficult to accomplish (Department of the Army Technical Manual TM9-1300-214, 1967). Nitrocellulose is extremely flammable and has a flash point-of 12.8°C. The melting point range Is 160* to 170'C — also its autolgnltlon temperature. "Guncotton", military grade cellulose nitrate, contains 13.5Z nitrogen and is the most highly nitrated form. Theoretically, mononitrated, dinitrated, and trinitrated cellulose contain 6.8Z N, 11.1Z N, and 14.1Z N, respectively. "Guncotton" is essentially fully nitrated and, therefore, can be considered to be a crude cellulose trinitrate contaminated by traces of less completely nitrated esters (Sullivan et al., 1978). The general properties of cellulose trinitrate are susmarized in Table II-l. The nitrate esters, in general, are soluble in esters, aldehydes, and ketones. The more completely nitrated a cellulose is, however, the smaller the range of materials in which It is soluble. The less nitrated forms of cellulose nitrate are also very soluble In methanol, benzene, toluene, and mixtures of ether and ethanol. These compounds (pyroxylin: 8Z to 12Z N and pyrocellulose: 12.5% N) are forms of collodion and are used chiefly as lacquers, ink bases, and filter membranes, and in veterinary medicine for wound closure. Cellulose trinitrate is insoluble in water, ethanol, ethyl ether, and benzene but completely miscible in acetone, methylethyl ketone, tetrahydrofuran, as well as nitrobenzene and ethyl-, butyl-, and amylacetstes (Sullivan et al., 1978). Nitrocellulose Is resistant to biological degradation and is a persistent compound in ths environment. It has been suggested by Sullivan et al. (1978) that cellulose trlscststs and cellulose trinitrate are reslstane to enzymatic attack. These authors further ststed that although direct blodegradatlon of nitrocellulose does not tees to bo feasible, alkaline hydrolysis yields material that can be decomposed by microbial activity. Nitrocellulose, therefore, .an be characterized as being persistent la the environment unless chemically altered. Based on aa extensive volume of literature dealing with the adsorptlve capacity of nitrocellulose for biologically Important macromolecules, Sullivan et al. (1978) have Indicated that nitrocellulose strongly adsorbs and concentrates DNA and various RNA molecules from solution, and adsorbs proteins, and polypeptides under-various conditions. Proteins with an uncoiled structure or molecular weight greater than 10 are strongly bound. Denatured proteins are also strongly adsorbed, especially under acidic conditions. II-1 ------- TABLE II-1 GENERAL CHEMICAL AND PHYSICAL PRCPERTIES OF CELLULOSE TRINITRATE3 CAS Number Names Molecular velghc Empirical formula Structure 9004-70-0 Cellulose trinitrate; nitrocellulose; guncotton Varies with chain length [C6H7°2(°N02)3]n mjCONO, HjCONO, N,C0*0, H ONO. m OMO, H CO, Color Physical state Specific gravity Percent nitrogen carbon oxygen hydrogen Solubility characteristics Melting point. Autoignitlott teaperatux* Flash polnfc Whitish Fibrous solid b/ 1.66 14.1 24.3 59.3 2.4 Iosoluabls in water* ethanol, benzene and most other solvents. Soluble in 25 parts of 1:3 alcohol:ether; soluble in acetone in all proporstions; soluble in methylethyl ketone, nitrobenzene, tetrahydVofuran, and ethyl, butyl and aaylacetate. 160-170* C 160-170* C 12.7* C References: Sullivan et si., 1978; Havley, 1981; RTECS, 1986. Approximate, depends on processing and chain length. 11-2 ------- III. SOURCES OF EXPOSURE Nitrocellulose (NC) is a principal ingredient of propellants, smokeless powder, rockee fuel, ball powder, mortar increments, and some explosives (Rosenblatt et al., 1973). It is produced for military use at selected Arav ammunition plants (AAP) by treating cotton linters or wood pulp with mixed nitric and sulfuric acids at 308C. The resulting slurry is centrifuged to remove cost of the acid, treated with several changes of boiling water, washed with a heavy stream of water, and finally screened to remove most of the water (Department of the Army Technical Manual TM9-1300-214, 1967). Production requires 16 to 22 gallons of process water per pound of NC produced. Most of this water is discharged and contains, la addition to NC, 0.7 to 1.0 pound of sulfuric acid ar.d 0.3 to 0.4 pound of nitric acid per pound of NC produced, thus resulting in a low pH (Rosenblatt et al., 1973; Helton, 1976). Nitrocellulose fines are found in production wastewater because of settling pit overflow and some escape after flowing through the waste acid neutralization process lines (Huff et al., 1975). Helton (1976) analyzed samples of NC fines from wastewaters of an AAP and found that more than 99Z of the particulate material was military grade NC with an average nitrogen content of 12.9Z and particle size greater than 5 microns. Sullivan et al. (1978) Indicated that these data suggested that suspended solids below 0.8 microns contained significant portions of nonnltrated cellulose and other materials while those greater than 44 microns were mostly NC. III-l ------- IV. PHAJ^-ACOKINETICS There art currently no available daca co suggest chat nitrocellulose ca-i be absorbed from any route. A study in rats has shown that NC appears to reaain within the gastrointestinal tract until it is excreted in the feces. Ccher available data are inconclusive. ^ Ellis ec al. (1976) studied the absorption, distribution, and excretion o£ C-nitrocellulose (prepared froo cotton grown in the presence of D-glucose-t'L- *C and nitrated by standard procedures) in two male Charles River CD rats. Each rat was fasted overnight before being given NC orally either in an aqueous suspension or in a suspension of 0.2Z methyl cellulose-O.4Z Tween 80 (MC-TW80) at a volume cf 1 ml/100 gm (presumably bodyveight; about 20,000 dpm/ml). After dosing, each rat was placed Immediately In a "Roth-Delmar" metabolism chamber. Expired CO , feces, and urine vera each collected separately In the apparatus. To ensure that sufficient radioactivity was administered, the dosing was repeated dally for 4 days. Twenty-four hours after the last dose, the animals were anesthetized and aortic blood was collected. Liver, spleen, brain, kidneys* lungs and thigh muscle along with the stomach, small Intestine, cecum, large intestine and their contents were removed and each assayed for radioactivity via liquid scintillation spectrometry. After repeaeed oral doses of radiolabeled nitrocellulose, no detectable radioactivity was found in any tissue or body fluid. Radioactivity was recovered only in the various components of the gastrointestinal (GI) tract plus contents and in the feces (percentage dpm recovered not specified). From these results, the authors concluded that the nitrocellulose molecule was not absorbed by the rat. Ellis et al. (1980) conducted a mass-balance metabolism study of nitrocellulose using a dog fed 90 g (mg/kg dose could noe be determined from data provided) of wet nitrocellulose (27.9 g dry weight). After 24, 48, 72 and 96 hours, the feces wera collected and analyzed by the method of Sellg (1961) which involves reduction of nitro groups and titration to a colorlmetrlc endpolnt. During the fIrst~48-hour period, 9.5 g (dry weight) of NC were recovered representing a recovery of 34Z (g recovered/g fed, dry weight). No further nitrocellulose vu Identified In later fecal samples. U« can draw no useful generalizations from these results since they could indlcaee either that the method of analysis vu not particularly effective, that soma nitrocellulose may have been abaorbad from Che dlgeatlve trace of this dog, or that NC was denitrated by gut bactarla. IV-1 ------- Currently available studies on the health effects of nitrocellulose suggest that it is not "toxic" unless ingested in enoraous quantities such as 10" of c-e total diet. In those cases, death from intestinal impaction may occur just as lc does in animals fed the same dietary levels of non-nitrated cotton linters. A. Short-Term Exposure The acute oral toxicity of nitrocellulose is very low in mice and rats as evidenced by LD 's of more than 5,000 mg/kg in both species. No acute toxicity data of nitrocellulose are provided in the 1986 edition of the Registry of Toxic Substances (RTECS, 1986). Lee et al. (I97S) used male and female Charles River rats and male and female albino Swiss mice (apparently 10/sex/dose; number and range of doses noe clearly specified) to determine the acute oral LD of nitrocellulose. Each dose of nitrocellulose, suspended in water ac a final concentration of SZ NC (dry weight basis), was divided in half and given 30 minutes apart due to the large volume necessary to administer a dose of 5,000 mg/kg (the authors did not indicate the volume administered). Test animals were fasted for at least 16 hours prior to oral dosing via gastric lntubaelon. After treatmene, the survivors were observed daily for 14 days for delayed mortality or signs of toxicity. The LD,_ was calculated by a computer program based on the method of maximum likelihood of Finney (1971). The LD^'s for nitrocellulose in male and female racs and in male and female mice were greater than 5,000 mg/kg. No toxic signs were observed in animals receiving the highest dose of nitrocellulose. Two of 10 male mice given 5,000 mg/kg died without any apparent gross lesions. No other animals died at any dose level. I. Primary Skin and Eye Irritation Using the modified Drslze method for skin and eye irritation, a 33Z concentration of NC in vater was applied directly to the eye or shaved skin of the rabbit and evaluated ac 24 and 72 hour* (Lee et al., 1975). This concentration of NC was noc Irritating to either rabbit skin or eye. B. Longer-Term Exposure 1. Thirteen-Week Studies No advert* effaces that cam be related to ths chemical characteristics of nitrocellulose wars Identified in the available thirteen-week studies In dogs, rats, and mice (Ellis et al., 1976). Intestinal blockage was the cause of death in high-dose mice (10Z NC) as wall as la control mice fed the same amount of cotton linters (10Z of total diet). ------- •His ec al. ( 1976) conducted thirteen-week studies of the oral tc~.i:.: nitrocellulose using dogs, rats and mice. In the studies with dogs, 20 vour.g healthy beagle dogs (7.2 to 13.6 kg) were divided into five groups of two a'aies and two females.. Three groups were administered NC as IX, 32, or 102 of their feed as dry weight. (Table Al-1, Appendix Al, describes method used to calculate doses. Using the authors' data for body weight at week 4 and average intake data for weeks 1 through 4, these doses were calculated to correspond to approximate iy 518, 1,900 and 6,890 og/kg/day, respectively, for males and 610, 2,976 and 8,485 rag/kg/day, respectively, for females.) The fourth group received a mixture of 10" (approximately 6,181 and 8,627 mg/kg/day, males and females, respectively, calculated as above) of cotton cellulose linters and served as a cotton control to determine if any observed effects were due to the passage of non-nutritive bulk through the gastrointestinal trace. The fifth group served as an untreated control. The tests included hematology, clinical blood chemistry and bromo- sulfophthalein (BSP) retention tests. Ac termination, the dogs were sacrificed and examined for treatment-related gross lesions and organs were weighed. Various tissues were processed for microscopic examination of lesions. Feeding NC to dogs at up to 10Z of their diets or cotton linters at 10Z for 13 weeks did not cause any adverse effects. Dogs fed 10Z NC or linters ate about 15Z more than the others* indicating the test materials were merely non-nutritive bulk. All dogs, including the uncreated and coccon controls, shoved some variations in body veighc, peripheral blood elemencs and various clinical chemistry tescs but all data were reported to be within normal limits. Nitrocellulose was not reported Co cause any ereacmenc-relaced gross or microscopic lesions. In thirteen-week studies vich racs, Ellis ee al. (1976) used 40 male and 40 female young healchy CD racs divided Into five groups, each consisting of eight males and eighe females. Three groups of racs were fed NC ae 1Z, 3Z, or l'OZ in the feed as dry veighc. The fourch group, che coccon concrols, vas fed cotton linters as 10Z of che feed. (Ref. Table Al-1: Using che authors' data for the body weights averaged from weeks 0, 4, 8 and 13 and che average intake over weeks 1 through 13* these dose* correspond to approximately 667 and 2,366 mg/kg/day for 1Z and 3Z» respectively, in che males and 820 and 2,673 mg/kg/day, respecclvely, in che feaalsa. Measured incakes for che racs fed 10Z NC or 10Z cotton linters in che diet war* more than double chose of che uncreaced concrol racs. The authors indicated that at 10Z NC or 10Z coccon llncers in che dlec, enormous mounds of whlce fluffy material were scattered all around the cage. Therefore, accual lncake of NC or cotton linters at 10Z in che diet cannot be calculated with any degree of accuracy.) Ths fifth group* the untreated controls* vas given the povdered standard rodent chov without NC. Experimental procedures vere similar to those used with dogs (Ellis et al., 1976) except that BSP retention tests were not performed. V-2 ------- Nitrocellulose arid the cotton linters at 102 in the feed apparent:-/ actec =s a non-nutritive bulk ingredient which the rats attenpted to remove. These rats gained less weight than did the untreated control rats. The authors concluded that this was because they did not absorb enough of the nutritive portion o: the feed. Rats fed the low or middle levels of NC apparently received enough nutritional intake and gained weight comparably to the untreated controls. Nitrocellulose administration did not result In any significant changes in peripheral blood elements or clinical blood chemistry or any apparent gross or microscopic lesions. Observed changes in the absolute organ weights of the liver, kidney and spleen of male rats fed 10Z NC or cotton linters were statistically significant when compared to untreated controls. These changes were attributed by the authors to depressed body weight gain, as evidenced by comparable organ weight/body weight ratios. In the thirteen-week studies with mice, Ellis et al. (1976) used 40 male and 40 female young healthy albino Swiss mice divided into five groups, each consisting of eight males and eight females. The treated groups were fed the same diets as prepared for the rats: 1Z, 3Z, or 10Z of NC as dry weight in feed. Control mice received either the powdered standard rodent chow alone (as untreated controls), or 10Z of cotton linters (as cotton controls). (Ref. Table Al-l: Using the authors' data for the body weights averaged froa weeks 0, 4, 8 and 13, and the average intake for weeks 1 through 13, these doses correspond to approximately 1,690 and 5,062 mg/kg/day for 1Z and 3Z, respectively, in males and 1,741 and 7,000 mg/kg/day, respectively, in females. As in the rat study previously described, the actual Intake of 10Z NC or 10Z cotton linters in the diet cannot be calculated with any degree of accuracy due to excessive scattering of the fibers.) The procedures used were similar to those described for rats except that clinical blood chemistry tests were not performed in mice. Blood samples for terminal hematology were collected by heart puncture under ether anesthesia. Mice fed the low, middle or high levels of NC showed no apparent adverse effects from the chealcal nature of this compound. In the first few weeks of the study, there were weight losses and deaths, apparently due to the fibrous nature of the substance. In mica fad the high level (10Z) of NC as wall as In mice fed 10Z of cotton llntera. The authors concluded that deaths were due to the blocking of tha lover part of tha gastrointestinal tract by masses of the fibers, particularly In tha regions where water is removed froa the chyme. Additional animals fro* a chronic study (saaa shipment and identical levels of NC) were added to this 13-vaek study to coapensate for tha early losses. No adverse effects or changes vara obaerved In peripheral blood elements nor were any treatment-related gross or microscopic lesions reported by the authors. 2. Lifetime Exposure Long-term studies conductsd in dogs, rata and mica Indicated a dose-related Increase in total feed consuaptlon and decreases in weight gain in high-dose V-3 ------- NC-created rats and mice. Histopathologic evaluations of dcgs, rats a-.i -_^e created for up to 24 aonths showed naturally occurring (as oppcsed :o treatment-related) lesions in the thyroid and lungs in dogs, the lur.gs in rats a-i several organs in mice (kidneys, adrenals, liver and intestines). Adverse effects causing early deaths due to intestinal impaction occurred in high-dose aice. Ellis ee al. (1980) studied the effects of NC administered orally at dose levels up to 10! NC in feed for dogs, rats and mice for 12 and 24 months. Three groups of beagle dogs, six of each sex per group, were administered NC at 1Z, 3Z or 10Z In the feed calculated on a dry weight basis for up to 24 months. (Ref. Table Al-1: Using the authors' data for the average body weight of 2 dogs/sex at 24 months and the average consumption [mean of 22 monthly measurements], these doses correspond co approximately 311, 1,013 and 4,070 tug/kg/day, respectively, for males and 344, 1,034 and 4,576 mg/kg/day, respectively, for females). Two addielonal control groups were run concurrently for each sex and were either untreated or received 10Z cotton linters (cellulose linters; approximately 2,888 and 3,874 mg/kg/day, males and females, respectively, when calculated as above) in their diets. No toxic signs related to NC intake were seen in any of the dogs ac any time. Following 12 months of treatment without a recovery period, one male and one female per treatment group were sacrificed. Hlstopathological examination revealed a variety of "minimal to mild lesions" in all. the dogs examined and moderate thyroid hyperplasia in a control and a high dose female and moderate thymus involution in a cotton control male. These lesions included microcalculi in the medula of the kidney, parafollicular cell hyperplasia of the thyroid, hemosiderosis of the spleen and axillary lymph nodes and involution of the thymus. The lesions were considered by the authors to be typical of those naturally occurring in dogs of the age tested and were, therefore, not considered treatment-related. Since there were no effects related to NC treatment, histologic data from the low and middle dose dogs were not evaluated, and the necropsy on the dogs in the recovery group (one/sex/treatment group) was omitted. No dose-related variations were reported for routine hematologic parameters nor in fasting blood glucose. serua transaminases (SCOT, SGPT), cholesterol, alkaline phosphatase sad blood urea nitrogen (BUM). The body weights, absolute and relative orgaa weights were comparable to unexposed controls or cotton controls (10Z linters). However* there was a dose-related Increase In feed consumption. Similarly, dog* (2/sex/treatment group) adalnlstered NC (up to 10Z) for 24 months (without s recovery period) showed what the authors considered naturally occurring histopathologic lesions. These lesions Included pituitary cysts, mild to severe chronic lymphocytic thyroiditis, pleural fibrosis, muscular hypertrophy of bronchioles, mild to moderate granulomatous pneumonia. renal calcinosis, extramedullary hematopolesls of the spleen and hemosiderosis of the lymph nodes. The absolute and relative orgaa weights had sons variations between individual dogs, but no apparent differences between dogs in different treatment groups. V-4 ------- 3ecause there were no observable effeccs froa feedirg N'C for 24 re-.:-.s, :-e necropsy on the dogs in the recovery group (2/sex/creacT.enc group) was cz.zzzd. Male and female racs (32/sex/treatment group) were similarly exposed to NC ac I", 3Z, or 10Z In the feed on a dry weight basis for up to 24 months (Ellis et al.t 1980). Controls, similar to those used in dog studies, were run concurrently. A separate group of raps, 8/sex/group, dosed as above, was started 6 months later and used for the one year necropsy and a 4-week recovery study. (Ref. Table Al-l: Using the authors' data for average terminal body weight at 24 months and the average consumption over 24 months [mean of 23 monthly measurements], these doses correspond to approximately 350 and 1,280 mg/kg/day for 1Z and 3Z, respectively, in males and to 373 and 1,422 mg/kg/day, respectively, in females.) Apparent feed intake for rats given 10Z NC or 10Z cotton linters was approximately twice by weight that of untreated controls. However, the authors Indicated that these two groups had visible scattering of feed and fiber around the cages. This scattering would account for part of the loss of weight in the feeders (the parameter measured) and, therefore, the apparent increased intake (actual intake of NC or cotton linters at 10Z in the diet) cannot be calculated with any degree of accuracy. Following 12 months of treatment, all exposed rats shoved a dose-related increase in food consumption. High dose and cotton control (10Z linters) male rats failed to gain weight or lose weight in the first week and, thereafter, gained weight more slowly than the controls. The authors felt that this effect was consistent with the face that NC serves as non-nutritive dietary bulk. Other than normal species variations, no significant effects ware apparent for routine hematologic parameters nor for fasting blood glucose, SCOT, SGPT, cholesterol, alkaline phosphaeasa and BUN. Absolute and ralaclva organ wcighes were generally comparable to controls with a few statistically significant differences (decrease in testes ac 3Z and spleen ae 3Z and 10Z, linters and controls in males). The authors reported thesa affects as normal variations. Upon histologic examination, mild to moderate chronic murine pneumonia was found in all unereaeed control rats, cotton control rats, and tha NC-treaced rata at ehe high dose levels. A variety of other lesions was found in ehase rats including bile duct hyperplasia and mild to severe nephritis In aalea only and cystic degeneration of the adrenal gland, and excessive hesoslderin in tha spleen of the females only. ' Tracheitis was wide-spread and slid to severe in nature. One 10Z cotton linters female displayed a fibroadenoma of the aaomary gland. Since the authors found no apparent relationahlp between NC feeding and the incidence or severity of any of these lesions* histologic data for low and middle dose rats were not evaluated and the necropsy after one month of recovery was omitted. It was further reported that in rats treated for 24 months, there were no statistically significant differencea in absolute and relative organ weights between treatment groups or when compared to controls. Upon histopathologic exaalnation, a large nuaber of lesions were found in various tissues of rats fed NC for 24 months without a recovery period but none were reported to be V-5 ------- significantly different froa controls. Some lesions, such as chronic r_r.-s pneumonia, were found in most rats. Other lesions were found less _f requer.:. • the variety and incidence of these lesions attributed co being t>pical of geriatric rata. The lesions included bile duct hyperplasia, foci or areas o: hepatocellular alteration, testicular degeneration and/or atrophy, senile nephropathy, nephritis or focal tubular nephrosis and mammary gland fibroadenoma, adenoma or adenocarcinoma. Hemosiderosis and/or extramedullary hematopoiesis of the spleen occurred almost twice as frequently in females than in males while myocardial degeneration and/or fibrosis were twice as frequent in males. Mo lesions were reported to be related, in Incidence or severity, to the NC dose administered. Similarly, lesions from rats fed NC for 24 months and allowed to recover for 1 month vera not considered to be NC-related. Also, in rats dying before the scheduled termination of the experiment (averaging between 40Z to 457. in males and females, respectively), there were no NC-related lesions reported. The cause of these early deaths was not addressed by the authors. Ellis et al. (1980) also studied the effects of NC administration in male and female mice (CD-I strain; 58/sex/group) at 1Z, 3Z or 10Z in the feed on a dry weight basis for up to 24 months employing procedures similar to those used for dogs and rats. Controls received either 10Z cotton llnters in the diet or regular chow. (Ref. Table Al-l: Using the authors' data for average terminal body weight at 24 months and the average consumption over 24 months [mean of 18 monthly measurements; measurements for months 4 to 7 vara omitted due to excessive scattering of feed ae all levels], these doses correspond to approximately 1,814 and 4,866 mg/kg/day at 1Z and 3Z, respectively, for males and 1,767 and 6,056 mg/kg/day, respectively, for females). As In the rat study previously described, the actual Intake of 10Z NC or 10Z cotton llnters in the diet could not be calculated with any degrea of accuracy due to what was described as an excessive scattering of tha fibers. As reported In tha previous study by Ellis et al. (1976), some early deaths (in tha first 3 weeks of the study) dua to Intestinal impaction by the fibrous material also occurred In miea fad tha high dosa (10Z) of NC and cotton control (10Z llnters) for up to 24 months. Gross necropsy found emboli of white fibrous material blocking tha inesstinas at various sites from tha jojunum downward. Additional mica, fad ths respective diets from tha start of tha study, were substltutad for th« dead mica. Tha hltffc flbsr contane of tha 10Z diets (cotton lintars and NC) was also reported am chs probable causa of an apparene irritation effece in these animals that firsr occurred la week 18 and decreased by tha end of month 10. This effect was charactarlxed by hyperemia of tha ears and eyelids, and subsequent edema of tha genitalis* fast and call accompanied by contlnuad scratching. This effect was not correlaced with any other toxic sign end was almosc non-existent in the lower treatmane levela and untreated controle. The effect was, therefore, attributed to tha physical, not chemical, nacura of the dlee. V-6 ------- In aice fed N'C for 12 -norths, the only scaciscical differences a-o-g ;<-e treatment groups (4/sex/level) were significant increases in weight of cne spLeen and ovaries, both absolute and relative to body and brain weight, in che cocton control females. Since similar increases were not seen at other necropsies nor were pathological lesions found, these increases were presumed by the authors to be normal variations, unrelated to treatment. Animals fed the 10Z diets (NC or linters) lost weight during the first week of the study but quickly began to gain, leveling off by A months, with average weights of all dosage groups converging during the second year. Upon histologic examination, male and female mice fed N'C at all levels for 12 months shoved a variety of lesions, usually degenerative or inflammatory. As is commonly seen in older mice, widespread amyloidosis of most tissues was observed, with deposits most heavily concentrated in the intestine and kidney. However, the authors indicated there was no consiseene relationship between any of the lesions and the NC treatment. Also, no treatment-related variations in the results of routine hematologic parameters, SGPT or BUN, were reported. In mice fed NC for 24 months with or without a recovery period, there were no treatment-related differences in organ weights, routine hematof&glc parameters, SCOT, SGPT nor BUM. Tissue lesions were found in mica fed the untreated control diet or high (10Z) NC dose and sacrificed after 24 months feeding, as veil as in those animals dying before that time. A variety of lesions, usually degenerative, were seen. Amyloid deposles, often heavy, were widespread. These were noe reported to be related to NC exposure. No histologic data were provided for control mice fed 10Z cotton linters. Due to a lack of ereatment related effects, no histologic data were provided for mice fed NC at 1Z and 3Z; nor were these data provided for treated mice allowed to recover for one month following NC treatment. At about month 9, many deaths (approximately 2SZ of the original number) with no apparent cause occurred in the high dose mice with a smaller number occurring in the cotton controls. A physical fiber effect was considered; however, since the death rata was three times higher In the NC-treatad mice, the authors felt that a compound effect of unknovn mechanism could not be dismissed. Rapid autolysis characteristic of aice precluded histopathological pxamlnatlon. C. Genetic Toxicology Studies have been conducted to determine the mutagenic potential of nitrocellulose employing bacterial assays as well as cytogenetic tests. Mutagenic activity was not detected using these bloassay systems under conditions of the tests. Ellis et al. (1978) conducted an Ames test exposing typhlmurlum tester strains TA1535, TA1537, TA1538, TA98 and TA100 to nitrocellulose at 100, 1,000 or 5,000 mlcrograas/plata for 48 hours. No statistically significant Increase in the number of revertant colonies was observed when compared to levels of spontaneous revsrtants either with or without S9 metabolic activation (added rodent liver homogenate). V- 7 ------- Ellis et al. ( 1976) studied the cytogenetic effects of \C on sonacii. cel. chromosomes employing peripheral blood lymphocyte and kidney cultures from racs fed NC at 10Z (mg/kg intake cannot be calculated due to excessive scatterirg of fibers) for 13 weeks. Treated rats did not show any changes in chromosome frequency distribution, number of tetraploids, or frequency of chromatid breaks, gaps or translocation in the test cultures when compared to cotton control (10" linters) cultures. No data on untreated controls was available for comparison. Ellis et al. (1980) reported that kidney and bone marrow cells from rats exposed to NC or cotton linters in the diet at 10Z (exact dose not calculated due to excessive scattering) for 2 years showed no numerical or morphological changes in chromosomes. D. Carcinogenicity Long-tern studies conducted in dogs, rats and mice indicated that the administration of NC in Che diet for up to 24 months did not significantly affect the incidence of tumors in various organs/systems in dogs, rats and mice when compared to control animals. Ellis et al. (1980) conducted 12 or 24 month feeding studies to determine the incidence of tumor formation following exposure to NC at up to 10Z in the diets of dogs, rats and mice. The studies described belov are the same as those described under "Lifetime Exposure" and are discussed more fully therein. Beagle dogs (6/sex/dose) were administered 1Z, 3Z or 10Z NC (Ref. Table Al— L: These doses correspond to approximately 311, 1,013 and 4,070 mg/kg/day, respectively, for males and 344, 1,034 and 4,576 mg/kg/day, respectively, for females, as described under Lifetime Exposure) for 12 to 24 months. Two additional groups were run concurrently for each sex and either remained untreated or received 10Z cotton linters in their diets. Following treatment, the animals were sacrificed and tissues were examined for occurrence of tumors in various organ systems. The authors reported no biologic variations or tumors in the test dogs. Rats, 32/sex/dose* were fed NC for up to 24 months at II, 3Z or 10Z in the diet (Ellis et al., 1980). (Ref. Table Al-1: These levels correspond to approximately 330 and 1,280 mg/kg/day for 1Z and 3Z, respectively, in males and 373 and 1,422 mg/kg/day, respectively, In females. Intakes for the 10Z level could nor be calculated.) Two additional groups were run concurrently for each sex and either vara untreated or received 10Z cotton linters. Following treatment, tha animal* ware sacrificed and evaluated histologically for tumor formation in various organ systems. The authors rsported the occurrence of pituitary chromophobe cell adenomas and various mammary tumors. Including fibroadenomas, adenomas, and adenocarcinomas/carcinomas at all dose levels. Thssa tumors also occurred in untreated and cotton controls. There waa a scattered incidence of many other v-a ------- naturally occurring tumor types In rats in all treatment and control grcu;s. lesions found ia various organ systems in SC-treated rats were attributed b .• ;-e authors to nitrocellulose. Ellis et al. (1980) also fed three groups of CD-I mice (58/sex/group) sc at IZ, 3Z or 10Z as dry weight in the feed for up to 24 months. (Ref. Table a 1-1: These levels correspond to approximately 1,814 and 4,866 mg/kg/day at IZ and 37., respectively, for males and 1,767 and 6,056 mg/kg/day, respectively, for females. Intake for the 10Z level could not be calculated.) Two additional groups were run concurrently for each sex and either were untreated or received 10Z cotton linters. Ac the end of the treatment period, the control and treated mice were sacrificed and tissues ware examined for occurrence of tumors in various organ systems. The authors reported the occurrence of bronchloalveolar carcinomas in control animals, but none vera observed In mice administered 10Z NC for 24 months. The absence of such tumors was statistically significant in males but not in females (P ¦ 0.004 for males, P ¦ 0.29 for females, P • 0.002 for the combined sexes, by exact analysis of the contingency table). However, the authors concluded that the difference probably represents natural variation and is toxlcologlcally meaningless. The slides from other dosage groups were not examined. E. Reproductive Effects Three-generation studies in rats indicated that NC administered alone in the diet at dose levels up to 10Z did not adversely affect reproduction. However, the increased inert bulk of 10Z fibers (NC or linters) may reduce the lactation index and pup velghe. Ellis et al. (1980) administered nitrocellulose in the diet of rats at 1Z, 3Z or 10Z in a three-generation study. (Ref. Table Al-1: These doses correspond to approximately 350 and 1,280 mg/kg/day for 1Z and 3Z, respectively, in males and 373 and 1,422 mg/kg/day, respectively, for females. The actual intake for the 10Z dose level cannot be calculated.) The initial groups of rats used as the parental (F ) generations were started at the sama time as the chronic study. Rats of each subsequent group* parents and offspring, received the sama control or NC-containlag dlata as their original PQ generation. First mating occurred when rats wera 8- aontha of aga. Following treatment, all offspring were examined at birth for gross physical abnormalities and the numbers of live and dead pups of each litta* vara racordad. Survival and body weighta wara recorded at 0, 4 and 21 days. Reproductiva performance for each parental and offspring generation was determlnad. The authora reported that the mean body weights at the time of first matlngs for males of all parental generations given diets containing 10Z NC were significantly reduced whan compared to males given untreated control diet. This reduction in body weight waa also significant in males and females fed cotton control (10Z linters) diets. V-9 ------- There were no indications chat the treacrents adversely a::e;ced :~a fertility of the males or females in the mating or pregnancy ratios. Fcr :-e " generation, most of these parameters actually suggested that either 102 NC or M1" cotton linters in the diet increased the fertility of rats given these treatrencs. However, this effect appears to be caused by the decreased fertility of the control Fq females. The fereilicy of the F^ females was similar to that of controls For groups given 1Z and 3Z NC (approximately 373 and 1,422 mg/kg/day). This decreased fertility in the control and low dose groups was attributed by the authors to both the age at time of first mating (8 months for all F parental generations) and body weights greater than that expected to give optimal reproductive performance. No treatment-related effects were apparent at any dose or in any generation on litter size, liveborn Index, birch weight, viability index, or the ratio of males to total offspring. Significant reductions In the lactation index and the weight of pups at weaning occurred with 10Z NC and 10Z cotton llnter controls. Reductions in these parameters were observed chiefly with the F through F litters for both groups but were not observed with the subsequent litters. 2^he authors attributed these reductions during lactation to relatively large amounts of inert bulk in a diet of 10Z fibers (NC or llnters). F. Teratogenicity Ellis et al, (1980) did not report conducting teratology studies. G. Immunologic Effects Ellis et al. (1976) studied the potential adverse effects of NC exposure on the immunologic response based on serum concentration of immunoglobulin (IgE) measured by the Immunodiffusion technique of Manclnl et al. (1964). The administration of 10Z NC la the feed to dogs or rats (this dietary level can be calculated, as described under Thirteen-Week Studies( to correspond to an average of approximately 7,690 mg/kg/day for dogs but could not be calculated for rats due to excessive scattering of fibers) for up to 13 weeks did not alter their serum concentrations of IgE* V-10 ------- VI. health advisory development Nitrocellulose, at doses averaging 4,300 ag/kg/day in dogs and in excess c: approximately 1,400 mg/kg/day in racs and 6,000 ng/kg/day in mice, was not coxic when fed for up to 24 months. The actual intakes in mg/kg/day in rats and mice fed 10Z NC could not be determined with any degree of accuracy due to visible scattering of the fibers around the cage. Assuming, however, that these animals consumed only tvice the amount of NC as those receiving the 3Z diet, a reasonably conservative estimate, Intake would be, at a minimum, approximately 2,800 mg/kg/day in rats and 12,000 mg/kg/day in mice. The only treatment-relaced effects in these high-dose,, long-term feeding studies were early weight loss in rats and mice and subsequent lower average body weights in the mature rat, hyperemia with edema of the ears, eyelids, genitalia, feet and tall apparently due to physical-mechanical effects of the fibers and death due to intestinal impaction in mice fed the 10Z diets (NC and cotton linters). The weight effect was attributed to the non-nutritive bulk of the fibrous diet and was confirmed by similar findings In control animals fed 10Z cotton linters (cellulose linters), the material that Is nitrated to form NC. This lower body weight, however, is not necessarily an adverse effect as the rodents fed the 10Z diets were characterized by less fat, not less lean body mass, when compared to untreated anlaals of the same species. This condition can, however, be detrimental If there la a very high body demand for nutrients, as during pregnancy and lactation. This condition occurred, to soma degree, in the early litters of the three-generation reproduction study in rats, as evidenced by a decreased lactation index and weight at weaning, but not in later generations, possibly indicating adaptation. The hyperemia with edema that occurred in mice was not life-threatening, resolved spontaneously and was of unknown cause. As this effect occurred in mice fed either 10Z NC or cotton linters and was accompanied by continuous scratching, a direct physical effect dua to irritation from contact with the fibers seems likely. Tha deaths dua to Intestinal impaction vara attributed 'to the relatively large slzs of eh* fibers In relation to tha size of tha luaen of the Intestines, allowing eh* asssas fomed by tha fibers to completely obstruct the gut. This effect occusrad la mica fad both the 10Z NC and cotton linters. Unresolved is a spate of death* of unknown causa that occurred at 9 months in both tha 10Z NC and cotton llat*rs groups but was at a higher level in the NC group. This may be due, In pare* e© tha chemical nature of NC. In 13-week feeding seudles ae tha eeae levels. Intakes averaged 7,700 mg/kg/day In dogs and were In exceaa of approximately 2,700 mg/kg/day in rats and 7,000 mg/kg/day In mica. Calculation of tha 10Z levels to approximates, as in the long-term study, would yield values, et e minimis, of 5,400 ng/kg/day la rats and 14,000 mg/kg/day In alee. There waa no evidence of toxicity. The Increased food VI-1 ------- consumption/decreased weight gain pattern in rats and 21.ce was similar :o z-.az - the Z^-month study, occurred at the 10T level in amr.als fed either S'C or c::ccr linters and was attributed to the non-nutritive bulk of the fibers. Death due to intestinal impaction also occurred in the high-dosed mice in this study and was.attributed to the physical nature of the fibers. Since the treated animals, like humans, cannot digest cellulose, passage of these fibers through the digestive tract would be expected. This non-digestion of the fibrous diet was confirmed in absorption studies. After repeated oral doses (once daily for four days) of radiolabeled nitrocellulose to rats, no detectable radioactivity was found in'any tissue or body fluid but was recovered only from various components of the GI tract, contents and feces. Nitrocellulose was noe mutagenic in either bacterial bloassays nor did it produce chromosome abnormalities in mammalian cells after in vivo exposure. It did noc significantly affect tumor incidence in dogs, rats and mice and produced only some adverse effects la rats with high nutrient requirements during pregnancy and lactation. In view of the non-eoxic nature of NC ae all doses seudled and its failure to be digested and absorbed In ch« species tested, health advisory (HA) values for 1-Day, 10-Days and Longer-term appear to b« unnecessary. Ie seems probable that, due to the fibrous nature of Che substance and Its insolubility in water, clarity or turbidity of tha water would be the only guideline necessary. vr-2 ------- VII. ANALYSIS Rosenblatt et al. (1973) in summarizing literature on the analysis of \C indicated that all analytical procedures probably would begin with collection of NC fibers from the water on filters. Weighing the filter is cited as a method co roughly estimate NC, but its accuracy would be limited by the presence of ir.erc solids. Other methods cited include: o Ferrous-titanous titration o Ferrous sulfate titration o Liberation of NO^ gas o Analysis of NH^ after reduction by Devarda's alloy o Transnitratlon of salicylate or citrate followed by ferrous-titanous titration o Chromous chloride-ferric ammonium sulfate micro-determination o Zinc dust reduction of the nitrate ester o Hydrolytlc liberation of nitrite ion in acetone Of the detection methods listed above, the last one is considered to be the most effective for detecting lov levels of NC In the environment (Sullivan et al., 1978; Rosenblatt et al., 1973). It Is a colorlmetrlc method based on hydrolytic liberation of nitrite by OH from acetone solutions of nitrate esters. The resulting NO^ is then dlazotlzed with either alpha-(naphthyl)-ethylenedlaolne hydrochloride or alpha-naphthylamine and the absorbance of the solution determined at 520 to 530 nm. The reaction Is not specific for NC; however, the insolubility of this compound In water allows quantitative separation from NO^, NO and other soluble nitrate esters or nitrocompounds In mixed wastewater by filtration or dialysis. Berkley and Rosenblatt (1978) adapted this procedure to the Technlcon Autoanalyzer. The procedure involves aspiration of a stirred NC suspension, dialysis against 9Z saline, and hydrolysis with 5N NaOH at 70s C for 10 minutes to release nitrite ion. Sulfanllle acid Is dlazotlzed by the nitrite ion at lov pH. The resulting dlaxonlua salt Is coupled with the N-(l-naphthyl)ethyleaediaaina, and the color produced Is measured at 520 nm. The limit of detactability la 0.4 ag/L of nitrocellulose. Sullivttet al.(1978) outlined two methods for determining NC in sediment. The first aathod Involves solvent extraction of the dried sediment In acetone or ethylacetaeas. The procedure la sensitive to as little as 0.5 mg/kg of nitrate ester; hovavar, It is not specific for NC because le also extracts other organic nitrate esters and nitrocompounds. The second method Involves an initial acetone extraction to reaove the nitrate ester. Nitrate Is then determined colorimetrlcally since le will oxidize ferrous Iron to ferric Iron after treating the extract with acetic acid, ferrous sulfate In sulfuric acid, and sodiua sulfite. Absorbance of the resulting yellow color is determined at 500 nm. This procedure, however, lacka sensitivity since the minimum detectable concentration in a 10 g sediment sample is 140 ag/kg. VII-1 ------- VIII. TREATMENT Wastewater from NC production facilities is neutralized, then settled, centrifuged, and/or screened to recover NC fibers (Sullivan et al., 1978). Cencrifugation leads to more efficient and constant recovery due to the high specific gravity of NC (Rosenblatt et al., 1973). The US Army Natick Laboratories (Massachusetts) has developed a chemical and microbiological process for the degradation of NC in wastewater (Rosenblatt et al.t 1973). The process Involves membrane ultrafiltration of the wastewater to concentrate the suspended NC. A 200-fold concentration, to a 3Z to 5Z NC suspension, was desired; however, only a 10-fold concentration, to 0.2Z NC, has been obtained by this process. The suspension is then treated with 3Z NaOH ac 90° to 95* C for 20 minutes to yield a soluble material containing little nitrate ester. After acid neutralization, nitrate escer content of the filtrate is determined by IR analysis. An extract of tha filter is similarly analyzed to detect any undissolved nltrata ester, presumably NC. The neutralized solution is mixed with domestic waste and fermented anaeroblcally to denitrify thus producing gaseous nitrogen as a produce. Methanol could be added as a nutrient in this step. The next step is an aerobic activated sludge treatment and finally, a second denltrification, again using methanol nutrient. The final product was reported to be nitrocellulose free. VIII-1 ------- IX. CONCLUSIONS A.VD RECOMMENDATIONS Based on available toxicity data and the chemical and physical properties of the compound* NC is apparently non-toxic to dogs, rats and mice and is noc digested nor absorbed in these species. These data, along with the relative insolubility of NC in vater, suggest that Health Advisory values for NC in drinking vater are unnecessary. The physical characteristics of the drinking vater as they relate to turbidity, clarity, caste and similar indicators of palatability appear to be the only guidelines necessary. A companion report, "Data Deficiences/Problem Areas and Recommendations for Additional Data Base Development For Nitrocellulose" (Appendix 2) summarizes the scope and adequacy of existing data reviewed for this HA and delineates those areas where additional data, if any, are deemed necessary. IX-1 ------- X. REFERENCES Barkley, J.J. and Rosenblatt, D.H., 1978. Automated nitrocellulose analysis. U.S. Army Medical Bioengineering Research and Development Laboratory Technical Report 7807, AD A067081, Fort Detrick, MD. Department of the Army Technical Manual TM9-1300-214, 7-7. 1967. Departments of the Army and the Air Force. Military Explosives. Nitrocellulose. Ellis, H.V., III et al., 1976. Mammalian toxicity of munitions compounds Phase II: Effects of multiple doses Part IV: Nitrocellulose. Report No. 5. 'Midwest Research Institute. Kansas City, MO, Contract No. DAMD-17-74-C-4073, AD A062016. Ellis, H.V., III et al., 1978. Mammalian toxicity of munitions compounds Phase I: Acute oral toxicity, primary skin and eye irritation, dermal sensitization, disposition and metabolism, and Ames tests of additional compounds. Report No. 6, Midwest Research Institute. Kansas City, MO, Contract No. DAMD-17-74-C-4073, AD A069333. Ellis, H.V., III et al., 1980. Mammalian toxicity of munitions compounds Phase III: Effects of life-time exposure Part III: Nitrocellulose. Report No. 9. Midwest Research Institute, Kansas City, MO, Contract No. DAMD-17-74-C-4073. Finney, O.J., 1971. Probit Analysis, Cambridge University Press. Hawley, G.G., 1981. The condensed chemical dictionary. Tenth edition. Van Nostrand-Reinhold. Helton, D.O., 1976. Chemical and physical characterization of nitrocellulose fines. Special Report. Midwest Research Institute, Kansas City, MO, Contract No. DAMD-17-74-C-4073. Huff, B.L. et al., 1975* Aquatic field surveys at Radford, Holston, Volunteer, and Milan Army anunition plants. Volume 1-Radford. Final Report. Wapora, Inc., Washington, D.C., Contract No. DAMD-17-74-C-4138. Lee, C.C. et al., 1975. Maanallan toxicity of munition compounds: Phase I. Acute oral toxicity* primary skin and eye irritation, dermal sensitization, and disposition and metabolism. Report No. 1. Midwest Research Institute, Kansas City, MO» Contract No. DAMD-17-74-C-4073, AD B011150L. Mancini, G. et al., 1964. Immunochemical quantitation of antigens by single radial immunodiffusion. Isaunocheaistry, 2:235. Rosenblatt, D.H. et al., 1973. Munitions production products of potential concern as waterborne pollutants-Phase I. U.S. Army Medical Environmental Engineering Research Unit Report No. 73-07, Edgewood Arsenal, MD. X-l ------- RTICS, 1986. Registry of Toxic Effects of Chemical Substances, Natioral Ir.sc:t-:e for Occupational Safety and Health (NIOSH). National Library of Medicine Online File. Selig, V., 1961. Microdetermination of aromatic nitro compounds, nitrocellulose, and cyclic nitramines. AEC Report l'CRL-6639:20-28. Sullivan, J.H. et al., 1978. A summary and evaluation of aquatic environmental data in relation to establishing water quality criteria for munitions unique compounds. Part I. Nitrocellulose. Final Report. U.S. Army Medical Research and Development Command Contract Number DAMD-17-77-C-7027, Water and Air Research, Inc., Gainsvlllc, FL. X-2 ------- APPENDIX 1 CALCULATION METHODS AI — 1 ------- IA3LE A1- 1 Calculation of Intake of Test Material (mg/kg/day) Intake • (a)(b)(1000) (100)(c) where: a • X NC In dlec b - intake of feed In grama/day* 1000 ¦ conversion factor, grams to milligrams 100 ¦ conversion factor, Z to grams/100 grams c - animal weight in kilograms* *Intake/animal weight data used may vary for each calculation depending upon information available in report. Text will describe exact conditions for determining these calculations for each experiment. Al-2 ------- APPENDIX 2 DATA DEFICIENCIES/PROBLEM AREAS AND RECOMMENDATIONS FOR ADDITIONAL DATA BASE DEVELOPMENT FOR NITROCELLULOSE A2-1 ------- TA3LE OF CONTENTS P-.CZ INTRODUCTION A2-3 OBJECTIVES A 2-3 BACKGROUND A2-3 DISCUSSION A2-4 CONCLUSIONS/RECOMMENDATIONS A2-5 REFERENCES A2-6 A2-2 ------- INTRODUCTION The Office of Drinking Water (ODW), Environmental Protection Agency (EPA), .a conjunction with the Department of the Army, has reviewed the available data on nitrocellulose (NC) for the purpose of developing a Health Advisory (HA) useful -.a dealing with contamination of drinking water, to include "state-of-the-art" information on health effects, analytical methodology and treatment technology. This information is contained in detail in the report entitled "Health Advisory on Nitrocellulose." OBJECTIVES The objective of this document is to provide an evaluation of data deficiencies and/or problem areas encountered in the review process for NC and to make recommendations, as appropriate, for additional data base development. This document is presented as an independent analysis of the currene status of NC toxicology, as related to its possible presence in drinking water, and includes a summary of the background information used in the development of the HA. For greater detail on the toxicology of NC, the original "Health Advisory on Nitrocellulose'* should be consulted. BACKGROUND Nitrocellulose is a non-volatile, fibrous, cotton-like, white solid used as a principal ingredient of propellents, smokeless powder, rocket fuel, mortar increments and some explosives (Sullivan et al., 1978). It is produced for military use at selected Army ammunition plants (AAP), and NC fines are found in production wastewater (Huff et al., 1975). It Is resistant to biological degradation and is* therefore, persistent In the environment and deemed a potential, if not known, contaminant in drinking water. The metabolism of NC as studied In rats (Ellis et al., 1976) Indicated that the compound remained in the gastrointestinal (GI) tract and was excreted unchanged. j Acute toxicity studies in rats and mice (Lee et al.* 1975) indicated that NC was nontoxic* with Upvalues greater than 5*000 mg/kg reported In both species. Thlrtcm-iraek (Ellis et al.. 1976) and 24-month (Ellis et al., 1980) feeding studies is threo specie* (dogs* rats and mlcs) gave no evidence of adverse or toxic effect* related to the chemical characteristics of NC; nor was NC found to be carcinogenic. The fibrous physical nature of NC. however* was the cause of early deaths duo to intestinal impaction In mice fed 10X NC or cotton linters in both tho 13-week and 24-aonth studies and was associatsd with an Increesed food lntske-decreaaed weight gain pattern in high dosed and cotton control rats and mica. The fibers were also reported to be the ciuse of a physical Irritation of the extremities of mica fed 102 NC or cotton llnter* aa evidenced by hyperemia and A2-3 ------- edema. A spate of deaths of unknown cause occurred in aice after nine -c-:-s o: feeding NC or cotton linters at 10Z in che diet. The number of deaths was his-er in che NC treated mice and may, therefore, be related to the chemical nature of the compound via a mechanism, as yet, undetermined (Ellis ec al., 1980). Nitrocellulose was reported to be non-mutagenlc in various indicator systems (Ellis et al., 1976, 1978, 1980). Three-generation reproduction studies in rats indicated thac NC did not adversely effect reproduction but that che non-nutritive bulk of the 10Z diet may cause an adverse effect during periods of high nucritlonal demand, such as pregnancy or lactation, as evidenced by a decrease in lactation index and weight at weaning (Ellis et al., 1980). No teratogenic studies were reported. Exposure to NC did not affect the immunological response of dogs or rats (Ellis «t al., 1976). Methods of analysis (Barkley and Rosenblatt, 1978) and treatment (Rosenblatt et al., 1973) adequate for detection and removal of NC at levels which mighc be deemed hazardous to health have been presented in detail in "Health Advisory on Nitrocellulose." The lack of toxicological indicators, along with the apparent non-absorptlon/non-dlgestion of tha NC fibers, led to the conclusion that HA values for NC in drinking water wera unnecessary. DISCUSSION Available data on the pharmacokinetics, health effects, analysis and NC wastewater treatment have been reviewed. While the available data on tha metabolism of NC are limited in scope, the chemical and physical nature of NC generally supports tha finding of tha one available study that NC passes through tha G1 tract apparently unchanged and unabsorbed. Additional studies would, therefore, ba unnecessary. Tha available studies on tha toxicity of NC include LD 's in rats and mice and short-tars (13 week) and longer-term (24 month) atudles in dogs, rats and mice that included asaesaaents for possible carcinogenicity. Three-generation reproductionatudle* in rats, mutagenicity aasaya in bacterial and cytogenetic systems an£lMBmologlcal studies in dogs and rats have also bean reported. All studies appear*adequate for use in HA development. Further lnveetigatloa of the causa of the spaea of deaths in mice occurring at nine months in the longer-ten feeding study sees warranted but, in vi*w of che otherwise low toxicity of >C along with the other available data, would not be necessary for HA developaea*. Teratogenic studies were not reported; however, tha apparent inability of MC to be absorbed would preclude its acting as a potential teratogen. Therefore, additional studies seem unnecessary at this time. A2-4 ------- Primary skin and eye irritation tests in rabbits were negative (Lee a: * •_ 1975). However, mice fed 10X N'C or cotton linters for up to 24 concns de-.el—ad edema and hyperemia of the extremities, apparently due to the fibrous nature of NC. More sensitive dermal studies, if available, would be appropriate but vculd ~ot be deemed necessary as regards contamination of the drinking water by NC. Several methods of analysis of NC in wastewater have been reported including a method adapted co the Technicon Autoanalyzer. The limit of detectability, 0.4 mg/L, appears adequate for determining drinking water contamination relative to palatability concerns. Methods for the treatmene of wastewater by chemical and microbiological degradation have been developed. The insolubility of NC in water and its ability to be removed by coagulation and/or filtration make it unlikely that more extensive treatment measures would be required. CONCLUSIONS/RECOMMENDATIONS Based on the above discussion, the following conclusions/recommendations can be made: 1. The available studies on NC toxicity are adequate for development of a HA useful in dealing with contamination of drinking water. 2. No significant data gaps or problem areas relative to NC in drinking water exist. 3. No further studies on NC, as relates to its possible presence in drinking water, are necessary at this time. A2-3 ------- RETICENCES Barkley, J.J. and Rosenblatt, D.H., 1978- Automated nitrocellulose analvsis. I'.S. Army Medical Bioenglneering Research and Development Laboratory Technical Report 7807, AD AQ67081, Fort Detrick, MD. Ellis, K. V., III ec al., 1976. Mammalian toxicity of munitions compounds Phase II: Effects of multiple doses Part IV; Nitrocellulose. Report No. S. Midwest Research Institute, Kansas City, MO, Contract No. DAMD-17-74-C-4073, AD A062016. Ellis, K.V., III et al., 1978. Mammalian toxicity of munitions compounds Phase I: Acute oral toxicity, primary skin and eye irritation, dermal sensitization, disposition and metabolism, and Aaes tests of additional compounds. Report No. 6, Midwest Research Institute, Kansas City, MO, Contract No. DAMD-17-74-C-4073, AD A060333. Ellis, H.V., III et al., 1980. Mammalian toxicity of munitions compounds Phase III: Effects of life-time exposure Part III: Nitrocellulose.p Report No. 9. 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U.S. Army Medical Research and nautili—ill fiwuil Contract Number DAMD-17-77-C-7027, Water and Air Research, Inc., Gain«viXl«, FL. A2-6 ------- |