August, 1988 ETHYLENE THIOUREA Health Advisory Office of Etinking Vtater U.S. Environmental Protection Agency I. INTRODUCTION Ihe Health Advisory (HA) Proqram, sponsored by the Office of Ctinkinn Water (OEW), provides information on the health effects, analytical method- ology and treatment technology that would be useful in dealinq with the contamination of drinking water. Health Advisories describe nonregulatory concentrations of drinkinq water contaminants at which adverse health effects would not be 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. Ihe. HAs are subject to change as new information becomes available. Health Advisories are developed for one-day, ten-day, longer-term (approximately 7 years, or 10% of an individual's lifetime) and lifetime exposures based on data describing noncarcinogenic end points of toxicity. For those substances that are kncwn or probable human carcinogens, accordinq to the Agency classification scheme (Group A or B), Lifetime HAs are not recommended. Ihe chemical concentration values for Group A or B carcinoaens are correlated with carcinogenic risk estimates by employing a cancer potency (unit risk) value together with assumptions for lifetime exposure and the consumption of drinking water. The cancer unit risk is usually derived from the linear multistage model with 95% 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, Wsibull, Logit or ftrobit 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 each model is based on differina assumptions, the estimates that are derived can differ by several orders of magnitude. ------- Ethylene Thiourea -2- Ajqust, 1988 II. GENERAL INFORMATION AND PROPERTIES Ethylene thiourea (ETU) is no longer used in canmerce but is a canmon degradation product of the ethylene bisdithiocarbamate (EBDC) pesticides. Although the toxicity of ETU may be similar to the toxic effects observed with the EBDCs, the One-day, Ten-day, Longer-term and Lifetime HAs for ETU should not necessarily be considered protective of exposure to individual EBDCs at this time. The mechanisms of toxicity for these substances are still under evaluation. CAS No. 96-45-7 Structural Formula H 2-Imidazolidinethione Synonyms ° ETU Uses 0 Degradation product of several EBDC pesticides. Properties Chemical Formula Molecular Weight Hiysical State (25°C) Boiling Ibint Melting Paint Density \fopor Pressure Specific Gravity Vfater Solubility (30°C) Log Octanol/Water ifertition C3H6N2S 102.2 Wiite crystals 203° 20 a/L Coefficient Taste Threshold Odor Threshold Occurrence ° ETU was not found in sampling performed at 264 ground water stations, according to the STORET database (STORET, 1988). ------- Ethylene Thiourea -3- August, 1988 Environmental Fate ° Ethylene thiourea can be deqraded by photolysis (U.S. EPA, 1982). # 14C-Ethylene thiourea was intermediately mobile (Rf 0.61) to very mobile (Rf 1.00) in muck and sandy loam soils, respectively, as determined by soil TLC (U.S. EPA, 1986a). Ajsorption was correlated to organic matter. Following 6 days of.incubation in dry silty clay loam soil, ETU residues were inmobile; however, ETU residues subjected to a wet-dry cycle were slightly mobile (Rf 0.2). ° Levels of ETU (purity unspecified) declined at an unspecified rate in sand, with a half-life of 1-6 days (U.S. EPA, 1986a). Concentrations of ETU declined frcm 220 ppra at day 0 to 116 ppm by day 1 and 86 ppm by day 6. ° Mancozeb has been shown to have a half-life of less than 1 day in sterile voter before degrading to ETU (U.S. EPA, 1982). The ethylene bisdithiocarbamates (EBDCs) are Generally unstable in the presence of moisture and oxygen, and the EBDCS decompose rapidly in water as well as in biological systems (U.S. EPA, 1982). 0 The EBDCs decompose rapidly in water. Mancozeb has been shown to have a half-life of less than 1 day in sterile water before degradinq to ETU (U.S. EPA, 1982). ° Riotolysis is a major degrading pathway for ETU (U.S. EPA, 1982). III. PHARMACOKINETICS Absorption 0 Allen et al. (1978) reported a very high rate of absorption of l^C-ETU gastrically administered at 40 mg/kg to female rhesus monkeys and female Sprague-E&wley rats. In both species, feces accounted for less than 1.5% of the excreted radioactivity at 48 hours after administration. ° Absorption was also high in male Sprague-E&wley rats orally administered 14c-ETU at 4 mgAg» with 82.7% of the total administered dose detected in the urine at 24 hours (Iverson et al., 1980). Distribution ° Allen et al. (1978) reported that in rhesus monkeys administered l^c-ETU at 40 mgAg by gastric intubation, total tissue distribution at 48 hours was apnroximately 25% of the administered dose; apDroximately half of that was concentrated in muscle, with measurable amounts noted in blood, skin and liver. In Sorague-C&wley rats, however, total tissue distribution was less than 1% of the administered dose. ° Except in the thyroid, ETU was not found to accumulate in rats qiven an oral dose (amount not specified) (U.S. EPA, 1982). Up to 80% of the absorbed dose was eliminated in the urine 24 hours after administration. ------- Ethylene Thiourea -4- August, 1988 Metabolism 0 Iverson et al. (1980) identified the 24-hour urinary metabolites of l^c-ETU orally administered to male Sprague-Dawley rats at 4 mg/kq. Imidazoline was present at 1.9% of the total recovered dose, imidazolone at 4.9%, ethylene urea at 18.3% and unchanged ETU at 62.6%. In female cats, intravenous (iv) administration of this dose resulted in uncharged ETU present in the urine at only 28% of the total recovered dose, with S-methyl ETU at 64.3% and ethylene urea at 3.5%. 0 One hundred percent of the ETU (dose not specified) fed to mice was recovered rapidly (time not specified) with 50% recovered in the urine (U.S. EPA, 1982). Of the urinary products, 52% was unchanqed ETU, 12% was ethylene urea, and 37% were polar products. 0 All animals that have been tested appear to metabolize EBDCs rapidly. ETU and ethylene bisdiisothiocyanato sulfide (EBIS) are the major metabolites formed (U.S. EPA, 1982). Approximately 7% of an EBDC dose is converted to CTU in vivo in the rat and 2% in the mouse (Nelson, 1987; Jordan and Neal, 1979). Excretion ° Allen et al. (1978) reported that 48 hours after qastric admini- stration of l^C-ETU at 40 mgAg to rhesus monkeys, approximately 55% of the administered dose was detected in the urine and 0.5% in the feces. In Sprague-Dawley rats dosed identically, 82% was recovered in the urine and 1.3% in the feces. 0 Iverson et al. (1980) reported that 82.7 and 80.6% of the total radioactivity of a single 4-mq/kg dose of ^C-ETU was eliminated in the 24-hour urine of orally treated male Sprague-Dawley rats and iv-treated female cats, respectively. HEALTH EFFECTS Humans 0 No suitable information was found in the available literature on the health effects of ETU in humans. Animals Short-term Exposure 0 The acute oral LD50 for ETU is 1,832 mg/kg in rats (U.S. EPA, 1982). 0 Graham and Hansen (1972) measured ^lj uptake in male Osborne-Mendel rats administered ETU (purity not stated) in the diet at 50, 100, 500 or 750 ppm for various time periods (e.g., 30, 60, 90 or 120 days). Assuminq that 1 ppm in the diet of younger rats is equivalent to approximately 0.1 mgAg/day (Lehman, 1959), these levels correspond ------- Ethylene Thiourea August, 1988 -5- to doses of about 5, 10, 50 or 75 mg/kg/day. Four hours after the injection of 131I, uptake was decreased significantly in rats that had ingested ETU at 500 or 750 ppm for all time periods. At 24 hours after 131i injection, uptake was significantly decreased in rats that had ingested 100, 500 or 750 ppm for all time periods. Histologically, the thyroid glands of rats ingesting ETU at approximately 5.0 mg/kg, the No-Cfciserved-Adverse-Effect Level (NDAEL) for this study, were not different from these of control rats. There was slight hyperplasia of the thyroid in rats given 100 ppm (10 mg/kg/day). At doses of 500 or 750 ppm (50 or 75 mg/kg/day), the thyroid had moderate to marked hyperplasia. ° In an 8-day maximum tolerated dose (MTD) study by Plasterer et al. (1985), dose levels of 0, 75, 150, 300, 600 and 1,200 mgAo ETU were given by gavaqe to mice (10/group, sex not specified). Body weiqht and mortality were evaluated. No significant effects were noted on body weight at the end of the eighth day. Based on mortality, ETU was considered moderately toxic by the authors. An MTD of 600 mgAd was determined. ° In a study by Freudenthal et al. (1977), ETU (>95% pure) was fed to rats (20/sex/group) in the diet at levels of 0, 1, 5, 25, 125 or 625 ppm for 30 days. Assuming that 1 ppm in the diet of a youno rat is equivalent to 0.1 mgAg (Lehman, 1959), these levels correspond to doses of about 0, 0.1, 0.5, 2.5, 12.5 or 62.5 mqAq* Thyroid function, food consumption, body weight gain and histopathology were assessed in the animals, tets in the 625-ppm qroups showed signs of toxicity after 8 days of exposure. Hair loss, dry skin, increased salivation and decreased food consumption and body weight gain were observed. Other effects noted in the 625-ppm dose group were decreased iodine uptake and percent triiodothyronine (T3) bound to thyrcglobulin. Thyroid-stimulating hormone (TSH) was increased, and T3 and thyroxine (T4) decreased in the 625-ppm dose group. Thyroid hyperplasia was also noted in this group. Aiimals exposed to 125 ppm exhibited increased TSH; decreased T4, and thyroid hyperplasia. Other thyroid parameters were not affected. Based on the absence of adverse effects in rats exposed to 25 ppm or less after 30 days, a NDAEL of 25 ppm (2.5 mg/kg) was identified. 0 Arnold et al. (1983) shewed that the thyroid effects of ETU (purity not stated) administered in the diet for 7 weeks to male and female Sprague-Dawley rats were reversible vtfien ETU was removed from the diet. Dose-related significant decreases in body weight and increases in thyroid weight were observed in all treated animals, starting at dose levels of 75 ppm (approximately 7.5 mgAg/day based on Lehman, 1959). This dose was identified as the lowest-Observed-Adverse-Effect Level (LQAEL) for this study. 0 In a 60-day study, which was a continuation of the above study by Freudenthal et al. (1977), 14/40 rats in the 625-ppm group died. Thyroid hyperplasia and altered thyroid function were observed in the two high-dose groups. Thyroid hyperplasia was also observed in the 25-ppm group. This effect, however, was not observed in this ------- Ethylene Thiourea August, 1988 -6- dose group when exposure was continued to 90 days. Thus, the NOAEL for this study is presumed to be 25 ppm, or 2.5 mgAg* Dermal/Ocular Effects 0 No information was found in the above literature on the dermal/ocular effects of ETU. Long-term Exposure 0 Freudenthal et al. (1977) described alterations in thyroid function and changes in thyroid morphology when Sprague-Dawley rats were administered ETU (96.8% pure) in the diet at levels of 1 to 625 ppm (approximately 0.1 to 62.5 mgAg/day based on Lehman, 1959) for up to 90 days. The NOAEL was reported to be 19.5 mg/kg/day at week 1 and 12.5 mgAg/day at week 12. • Graham and Hansen (1972) measured 131I uptake in male Osborne-Mendel rats administered ETU (purity not specified) in the diet at 50, 100, 500 or 750 ppm for up to 120 days. Assuming that 1 ppm in the diet of older rats is equivalent to aoproximately 0.05 mg/kg/day (Lehman, 1959), these dosages are equivalent to approximately 2.5, 5, 25 and 37.5 mgAg/day. Four hours after the injection of radioactive iodine, uptake was decreased significantly in rats ingesting ETU at 500 or ' 750 ppm (25 or 37.5 mgAg/day) for all feeding periods. At 24 hours after 13*1 injection, uptake was significantly decreased in rats ingesting the 100-, 500- and 750-ppm doses for all feeding periods. Histologically, the thyroid glands of rats ingesting ETU at approximately 2.5 mg/kg, the NDAEL for this study, were not different fran those of control rats. Ihere was slight hyperplasia of the thyroid in rats given 100 ppm (5 mg/kg/day). At doses of 500 or 750 ppm (25 or 37. 5 mgAg/day), the thyroid had moderate to marked hyperplasia. 0 The thyroid appears to be the primary target organ for ETU toxicity in longer-term exposure studies. (Sraham et al. (1973) measured 131i uptake in male and female Charles River rats fed ETU (purity not specified) in the diet at 0, 5, 25, 125, 250 or 500 ppm for up to 12 months. Assuming that 1 ppm in the diet of older rats is equivalent to approximately 0.05 mg/kg/day (Lehman, 1959), these levels corresTOnd to doses of about 0.25, 1.25, 6.25, 12.5 or 25 mgAg/day. Adverse effects were noted at 2, 6 and 12 months. At 12 months, significant decreases in body weight and increases in thyroid weight were seen at the 125-, 250- and 500-ppm levels. Ujptake of 13*1 was significantly decreased in male rats after 12 months at 500 ppm, but was increased in females. Microscopic examination of the thyroid revealed the development of nodular hyperplasia at dose levels of 125 ppm and higher. The NDAEL for thyroid effects in this study *as 25 pnm (approximately 1.25 mgAg/day). ° Ulland et al. (1972) reported a dose-related increased incidence of hyperplastic goiter in male and female rats fed ETU at 175 and 350 pnn in their diet for 18 months (approximately 8.75 and 17.5 mg/kg/day, based on Lehman, 1959). An increased incidence (significance not specified) of simple goiter was also reported in all treatment groups. ------- Ethylene Thiourea -7- August, 1988 ° In a 2-year study by Qraham et al. (1975)/ Charles River rats were fed ETU (purity not specified) in the diet at 0, 5, 25, 125, 250 or 500 ppn (approximately 0.25, 1.25, 6.25, 12.5 or 25 mg/kg/day, based on Lehman, 1959). Statistically significant (p <0.01) decreases in body weight were observed in both sexes fed at 500 ppm. Increases in thyroid-to-body weight ratios were apparent at 250 and 500 ppn (p <0.01). Ihere was an increased iodine (131I) uptake at 5 ppm and a decreased uptake at 500 ppm, as well as slight thyroid hyperplasia at the 5- and 25-ppm dose levels (significance not stated). Based on these results, a LOAEL for lifetime exposure of 5 ppm (0.25 mgAg/day) was identified. Reproductive Effects 0 Plasterer et al. (1985) administered ETU (purity not specified) by gavage as a water slurry to CD-I mice at 600 mgAg/day on days 7 to 14 of gestation. At this dose level, maternal toxicity was not observed but the reproductive index was significantly decreased (p <0.05), indicating severe prenatal lethality. 0 New Zealand Wiite rabbits were dosed with ETU (100% pure) at 10, 20, 40 or 80 mgAg/day on days 7 to 20 of pregnancy (Khera, 1973). Observed effects included an increase (p <0.05) in resorption sites at 80 mq/kg. fb adverse effects on fetal weight or on the number of viable fetuses per pregnancy were noted at any dose level, and no signs of maternal toxicity were observed. Based on the results of this study, a NOAEL of 80 mg/kg/day for maternal toxicity and a NOAEL of 40 mg/kg/day for fetotoxicity were identified. Developmental Effects 0 The ability of ETU to induce various adverse effects, including teratogenicity and maternal toxicity, has been demonstrated by several investigators using various animal models. Available data indicate that rats are probably the most sensitive species. 0 Wiera (1973) orally administered ETU (100% pure) to Wistar rats at daily doses of 5, 10, 20, 40 or 80 mg/kg fran 21 or 42 days before conception to pregnancy day 15 and on days 6 to 15 or 7 to 20 of pregnancy. Dose-dependent lesions of the fetal central nervous and skeletal systems were produced, irrespective of the time at which ETU was administered. Teratogenic effects seen at the two highest dose levels included meningoencephalocele, meningorrhagia, meningorrhea, hydrocephalus, obliterated neural canal, abnormal pelvic limb posture with eguincvarus, micrognathia, oligodactyly* and absent, short or kinky tail. less serious defects were seen at 20 mgAdf and at 10 mgAg there was only a retardation of parietal ossification and of cerebellar Purkinje-cell migration. Retarded parietal ossification was the only abnormality seen at 5 mq/kg (significance not stated), its incidence being limited to small areas and to a few large litters. Nd signs of maternal toxicity were observed in rats administered ETU at 40 mgAg/day for 57 days (42 days preconception to day 15 of gestation). Based on the results of this phase of the study, the ------- Ethylene Thiourea -8- August, 1988 NOAEL for nvaternal toxicity was 40 mq/kg/day, and the NOAEL for developmental effects was 5 mgAg/day. ° In the same study (Khera, 1973) New Zealand White rabbits were dosed with ETU at 10, 20, 40 or 80 mg/kg/day on days 7 to 20 of pregnancy. Observed effects included a reduction in fetal brain:body weight ratio at 10 and 80 mg/kg (p <0.01). Renal lesions, characterized by degeneration of the proximal convoluted tubules, were noted micro- scopically {dose level not specified), but there were no skeletal abnormalities that were attributed by the authors to ETU. Ihe results of this study are not useful for determining a NOAEL or DDAEL. 0 Ebse-related central nervous system (CNS) lesions in Wistar rat fetuses were reported by ttiera and Iryphonas (1985). Ethylene thiourea (>98% pure) was administered by gastric intubation at 0, 15 or 30 mg/kg to dams on day 13 of pregnancy. Observed lesions at 30 mg/kq included histopathologic^ changes of the CNS such as karyorrhexis in the germinal layer of basal lamina extending frcm the thoracic spinal cord to the telencephalon, and obliteration and duplication of the central canal and disorganization of the germinal and mantle layers. In the brain, the ventricular lining was fully denuded, neuroepithelial cells were arranged in the form of rosettes and nerve cell proliferation was disorganized. In the 15-roq/kg/day qroup, cellular necrosis was less severe and consisted of small groups of cells dispersed in the germinal layers of the neuraxis. tone of the dams treated with ETU at any level in this study showed any overt signs of toxicity. Based on the results of this study, the NOAEL for maternal toxicity was 30 mgAg and the LOAEL for developmental toxicity was 15 mg/kg. ° Sato et al. (1985) investigated the teratogenic effects of ETU (purity not specified) on long-Evans rats exposed by gastric intubation to a single dose of 80, 120 or 160 mg/kg on one day between days 11 and 19 of gestation. Fetal malformations were related to both the day of administration and the dosage level. A short or absent tail was noted, for exanple, in 100% of fetuses exposed to ETU on gestational day 11 to 14. On day 11, a dose-dependent incidence of spina bifida and myeloschisis with hind-brain crowding were observed. A high incidence (48 to 87.5%, not dose-related) of macrocephaly with occipital bossing was noted, with administration of ETU on day 12, and an almost total incidence (96 to 100%} with administration on day 13. Other abnormalities seen in this study were exencephaly, microcephaly and hypognathia, and extremely high incidences (100% in many groups) of hydroencephaly and hydrocephalus, especially associated with administration days 14 through 19. Maternal toxicity was not addressed by the authors. Ihe results of this study are not useful in determining IDAELs or NDAELs for teratogenicity or maternal toxicity, but serve instead as evidence of the kinds of developmental effects that a single dose of ETU at 80 mgAg can induce teratogenic effects in rats. ° Khera and Iverson (1978) reported that there was no clear evidence of teratogenicity in kittens whose mothers had been administered ETU (purity not specified) at 5, 10, 30, 60 or 120 mgAg by gelatin capsule for days 16 to 35 of gestation. However, fetuses from cats in a ------- Ethylene Thiourea -9- August, 1988 moribund state subsequent to ETU toxicosis (30 to 120 mq/kq dosage groups) did show a high incidence (11/35) of malformations including colobana, umbilical hernia, spina bifida and cleft palate. Maternal toxicity and death were observed at dose levels of 10 mqAg and abcwe, manifesting signs of toxicity that were delayed in onset and characterized by progressive loss of body weight, ataxia, tremors and hind-limb paralysis. In this study, the NDAEL for maternal toxicity was identified as 5 mgAg/day and the NDAEL for developmental effects was 10 mg/kg/day. 0 Chemoff et al. (1979) demonstrated the teratogenic effects of ETU in Sprague-Dawley rats, CD-I mice and golden hamsters. The rats were administered ETU (purity not specified) by gastric intubation at 80 mg/kg/day on days 7 to 21 of gestation. Gross defects of the skeletal system (micrognathia, micramelia, oligodactyly, kyphosis) and the CNS (hydrocephalus, encephalocele), as well as cleft palate were noted in a majority of fetuses at this dose level, tto clear evidence of teratogenicity was seen in groups of rats administered dose levels of 5 to 40 mgAg/day. Nd similar pattern of defects was observed in CD-I mice dosed at 100 or 200 mgAg/day on days 7 to 16 of gestation or in golden hamsters dosed at 75, 150 or 300 mq/kg/day on days 5 to 10 of gestation. Observations of maternal toxicity included a marked decrease in the average weight qain of pregnant rats dosed at 80 mg/kg/day (p <0.001). Nb significant effects were observed in mice or hamsters. Based on the results of this study, the NOAELs for maternal and developmental toxicity were 40 mg/kg/day in the rat, 200 mg/kg/day in the mouse and 300 mq/kq/day in the hamster. 0 Adverse developmental effects of orally administered ETU, including teratogenicity and/or maternal toxicity, have been reported at 60, 100 and 240 mg/kg in rats (Khera, 1982; Teramoto et al., 1975; Ruddick and Wiera, 1975) and at 400 and 1,600 to 2,400 mg/kg in mice (Teramoto et al., 1980; Khera, 1984). Mutagenicity 0 Seiler (1973) described ETU as exhibiting weak but significant mutagenic activity in Salmonella typhimurium HIS G-46. A 2.5-fold increase in mutation frequencies (p <0.001) was seen at intermediate concentrations (100 or 1,000 ppm/plate), but at higher concentrations (10,000 and 25,000 ppm) ETU was somewhat lethal to the test colonies resulting in lower relative mutagenic indices (1.60 and 1.16, respectively). ° Schupbach and Hurcmler (1977) reported that ETU induced mutations of the base-pair substitution type in £3. typhimurium TA 1530 in vitro as well as in a host-mediated assay. In the host-mediated assay, a dcse of 6,000 mg/kg (LO5Q = 5,400 mg/kg) resulted in a sliqht but significant increase of the reversion frequency by a factor of 2.37. Results of a micronucleus test were negative after twofold oral administrations of 700, 1,850 or 6,000 mq/kg to 9wiss albino mice; it was concluded that ETU does not induce any chrcmoscmal anomalies ------- Ethylene Thiourea -10- August, 1988 in the bone marrow. Nd daninant-lethal effect was deserved after single oral closes of 500, 1,000 or 3,500 mg/kg were qiven to male mice. Carcinogenicity 0 Qraham et al. (1975) reported that ETU was a follicular thyroid carcinogen in male and female Charles River rats that were fed the compound (purity not specified) for 2 years at dietary levels of 250 and 500 ppm (approximately 12.5 and 25 mg/kg/day based on Lehman, 1959). 0 In a survey of several compounds for tumorigenicity, Innes et al. (1969) reported that ETU (purity not stated) administered by diet to two strains of specific pathoqen-free hybrid mice at a daily dosage of 215 mg/kg/day for 18 months resulted in statistically significant (p <0.01) increases in hepatomas (14/16 or 18/18 for males and 18/18 or 9/16 for females) and in total tumor incidence. Pulmonary tumors and lymphomas were also investigated, but were not found to occur in the ETU group. Ihe thyroid was not evaluated in this study. No other dose level was tested. 0 Ebse-related incidences of follicular and papillary thyroid cancers with pulmonary metastases and related lesions such as thyroid solid- cell adenomas were reported in Charles River CD rats by Ulland et al. (1972). Ethylene thiourea (97% pure) vas administered by diet for 18 months at 175 or 350 ppm folloed bv administration of a control diet for 6 months. Assuming that 1 ppm in the diet of older rats is equivalent to approximately 0.05 mq/kg/day (Lehman, 1959) these levels correspond to doses of about 8.75 and 17.5 mg/kg/day. Ihe first tumor was found after 68 weeks, and most were detected after 18 to 24 months vrfien the study was terminated. Ihe statistical significance of the reported findings was not addressed. V. QUANTIFICATION OF TOXIGOLOGICAL EFFECTS Health Advisories (HAs) are generally determined for one-day, ten-day, longer-term (up to 7 years) and lifetime exposures if adequate data are available that identify a sensitive noncarcinogenic end point of toxicity. Ihe HAs for noncarcinogenic toxicants are derived using the following formula: HA = (N3AEL or IQAEL) x (BW) - mg/L ( uq/L) (UF) x ( I/day) where: NOAEL or IOAEL = No- or Lowest-Observed-Adverse-Effect Level in mgAg bw/day. BW = assumed body weight of a child (10 kg) or an adult (70 kg). ------- Ethylene Thiourea august, 1988 -11- UF = uncertainty factor (10, 100, 1,000 or 10,000), in accordance with EPA or NAS/ODW guidelines. L/day = assumed daily water consumption of a child (1 L/day) or an adult (2 L/day). One-day Health Advisory Nd data located in the available literature were suitable for determination of the One-day HA value. It is therefore recamended that the Ten-day HA value for the 10-kg child (0.3 mq/L, calculated below) be used at this time as a conservative estimate of the One-day HA value. Ten-Day Health Advisory The study by Freudenthal (1977) has been selected to serve as the basis for determination of the Ten-day HA for a 10-kg child. ETU was fed to a group of rats (20/sex/group) for up to 90 days at levels of 0, 1, 5, 25, 125 or 625 ppm (0, 0.1, 0.5, 2.5, 12.5 or 62.5 mg/kg/day assuming that 1 ppm in the diet of a young rat equals 0.1 mq/kg/day, based on Lehman, 1959). Toxic effects on thyroid function and morphology were observed after 30 days' exposure to 125 pnm or greater. Nb adverse effects were noted in the 25-ppm group (2.5 mg/kg). Developmental effects reported in other studies have been reported in rats exposed in utero at 5 mq/kg (delayed parietal ossification) (ttiera, 1973). The adversity ofthis effect is unclear. Wiera and Iverson (1978) have reported maternal toxicity and death in cats exposed to 10 mq/kq. Therefore, 2.5 mg/kg was selected as a conservative NDAEL for derivinq the Ten-day HA. Using the NDAEL of 2.5 mg/kg/day, the Ten-day HA for a 10-kg child is calculated as follows: Ten-day HA = (2.5 mqAq/day) (10 kg) = 0.25 mgA (300 uqA) (100) (1 L/day) vdiere: 2.5 mg/kg/day = NDAEL, based on absence of fetal or maternal toxicity in rats exposed to ETU for 30 days. 10 kg = assumed body weight of a child. 100 = uncertainty factor, chosen in accordance with EPA or NAS/ODW guidelines for use with a NDAEL from an animal study. 1 L/day = assumed daily water consumption of a child. Longer-term Health Advisory Ihe study by Qraham et al. (1973) has been selected to serve as the basis for determination of the Longer-term HA. In a 12-month study, 131j uptake was measured in male and female Charles River rats fed ETU (purity not specified) in the diet at 5, 25, 125, 250 or 500 ppm for 2, 6 or 12 months. ------- Ethylene Thiourea -12- August, 1988 Assuming that 1 ppm in the diet of older rats is eauivalent to approximately 0.05 mg/kg/day (Lehman, 1959), these levels correspond to doses of about 0.25, 1.25, 6.25, 12.5 or 25 mgAg/day. Adverse effects were noted at all three test intervals. At 12 months, significant decreases in body weight and increases in thyroid weight were seen at the 125-, 250- and 500-pom levels. Ubtake of ^"ll y^g significantly decreased in male rats after 12 months at 500 ppm but was increased in females. Microscopic examination of the thyroids revealed the development of nodular hyperplasia at dose levels of 125 ppm and higher. The NOAEL for thyroid effects in this study was 25 ppm (approximately 1.25 mg/kg/day). The Longer-term HA for a 10-kg child is calculated as follows: Longer-term HA = (1*25 mg/kg/day) (10 kg) = 0.125 mg/L (100 ug/L) (100) (1 L/day) vrfiere: 1.25 mgAg/day = NOAEL, based on absence of thyroid effects in male rats exposed to ETU in the diet for up to 12 months. 10 kg = assumed body weight of a child. 100 = uncertainty factor, chosen in accordance with EPA or NAS/ODW guidelines for use with a NOAEL frcm an animal study. 1 L/day = assumed water consumption by a 10-kg child. The Longer-term HA for a 70-kg adult is calculated as follows: Longer-term HA = 1.25 mgAg/day) (70 kg) = 0.44 mgA (400 ugA) (100) (2 L/day) where: 1.25 mg/kg/day = NOAEL, based on absence of thyroid effects in male rats exposed to ETU in the diet for up to 12 months. 70 kg = assumed body weight of an adult. 100 = uncertainty factor, chosen in accordance with EPA or NAS/ODW guidelines for use with a NOAEL frcm an animal study. 2 l/day = assumed daily water consumption by an adult. Lifetime Health Advisory Ihe Lifetime HA represents that portion of an individual's total exposure that is attributed to drinking water and is considered protective of noncar- cinogenic adverse health effects over a lifetime exposure. The Lifetime ha ------- Ethylene Thiourea -13- August, 1988 is derived in a three-step process. Step 1 determines the Reference Ebse (RfD), formerly called the Acceptable Daily Intake (ADI). The RfD is an esti- mate of a daily exposure to the human population that is likely to be without appreciable risk of deleterious effects over a lifetime, and is derived frcm the NOAEL (or LOAEL), identified frcm a chronic (or subchronic) study, divided by an uncertainty factor(s). From the RfD, a Drinking W&ter Bauivalent Level (EWEL) can be determined (Step 2). A DWEL is a medium-specific (i.e., drinkinq water) lifetime exposure level, assuming 100% exposure from that medium, at vrfiich adverse, noncarcinogenic health effects would not be expected to occur. The DWEL is derived from the multiplication of the RfD by the assumed body weight of an adult and divided by the assumed daily water consumption of an adult. Ihe Lifetime HA is determined in Step 3 by factoring in other sources of exposure, the relative source contribution (RSC)., Ihe RSC frcm drinking water is based on actual exposure data or, if data are not available, a value of 20% is assumed. If the contaminant is classifed as a Qroup A or B carcinogen, according to the Agency's classification scheme of carcinogenic potential (U.S. EPA, 1986b), then caution should be exercised in assessinq the risks associated with lifetime exposure to this chemical. Ihe study by Qraham et al. (1975) was selected as the most appropriate basis for the calculation of a EWEL. In this 2-year study (presumably a continuation of the Qraham et al. (1973) study, Charles River rats were fed ETU (purity not stated) in the diet at 5, 25, 125, 250 or 500 ppm (approxi- nately 0.25, 1.25, 6.25, 12.5 or 25 mg/kg/day based on Lehman, 1959). Statistically significant (p <0.01) decreases in body weight were observed in both sexes fed at 500 ppm. Increases (p <0.01) in thyroid-to-body veiqht ratios were apparent at 250 and 500 ppm. There was an increased iodine (*31I) uptake at 5 and 125 ppm and a decreased uptake at 500 ppm as well as slight thyroid hyperplasia at the 5- and 25-ppnt dose levels (statistical significance not stated). Ihis effect is considered to be biologically significant. Tumors were evident in animals in the 125-ppm group. Based on these results, the LOAEL for lifetime exposure was identified as 5 ppm (approximately 0.25 mg/kg/day). Using the D0AEL of 0.25 mq/kg/day, the EWEL is calculated as follows: Step 1: Determination of the Reference Dose (RfD) RfD = (0.25 mqAq/day) = 0.000025 mg/kg/day (0.03 ug/kq/day) (1,000) (10) where: 0.25 mg/kg/day = LOAEL, based on increased iodine intake as well as thyroid hyperplasia in rats exposed to ETU in the diet for 2 years. 1,000 = uncertainty factor, chosen in accordance with EPA or NAS/ODW guidelines for use with a LOAEL from an animal study. 10 = additional uncertainty factor to account for the severity of effect and response at this dose level. ------- Ethylene Thiourea August, 1988 -14- Step 2: Determination of the Etinking water Equivalent Level (EWEL) DWEL = (0.00003 mqAq/day) (70 kg) = 0.00105 mg/L (1 ugA) (2 L/day) vtfiere: 0.00003 mg/kg/day = RfD. 70 kg = assuned body weight of an adult. 2 L/day = assumed daily water consumption of an adult. Step 3s Determination of the Lifetime Health Advisory According to EPA's guidelines for assessment of carcinogenic risk (U.S. EPA, 1986b), ETU is classified in Group B: Rrobable human carcinogen. Therefore, a Lifetime Health Ajvisory is not recamended for ETU. The estimated cancer risk level associated with lifetime exposure to ETU at 1 ug/L is approximately 4.3 x 10~®. Evaluation of Carcinogenic Potential 0 Three studies that evaluated the carcinogenic potential of ETU were identified. The results of these studies indicate that ETU is a- thyroid carcinogen in rats (Gtaham et al., 1975; Ulland et al., 1972) and increases the incidence of hepatomas as well as total tumor incidence in mice (Innes et al., 1969). 0 Graham et al. (1975) reported ETU to be a thyroid carcinoqen in male and female Oiarles River rats that were fed the compound (Duritv not specified) for 2 years at dietary levels of 250 and 500 ppm (approxi- mately 12.5 and 25 mg/kg/day in the diet of older rats based on Lehman, 1959). At 125 ppm (approximately 6.3 mg/kg/day), ETU was a thyroid oncogen. ° Dose-related incidences of follicular and papillary thyroid cancers with pulmonary metastases and related lesions such as thyroid solid- cell adenomas were reported in Charles River CD rats by Ulland et al. (1972). Ethylene thiourea (97% pure) was administered in the diet for 18 months at 175 and 350 ppm followed by administration of a control diet for 6 months. Assuming that 1 ppm in the diet of older rats is equivalent to approximately 0.05 mg/kg/day (Lehman, 1959), these levels correspond to doses of about 8.75 and 17.5 mg/kg/6ay. The first tumor was found after 68 weeks, and most were detected after 18 to 24 months when the study was terminated. The statistical significance of the reported findings was not addressed. 0 Innes et al. (1969) reported that ETU (purity not stated) administered by diet to specific pathogen-free hybrid mice at a daily dosage of 215 mgAg/day for 18 months resulted in statistically significant (p <0.01) increases in hepatomas and in total tumor incidence. No other dose level was tested. (Pulmonary tumors and lymphomas vere also investigated in this study.) ------- Ethylene Thiourea August, 1988 -15- 0 Applying the criteria described in EPA's final guidelines for assess- ment of carcinogenic risk (U.S. EPA, 198(b), ETU may be classified in Group B2: probable human carcinogen based on sufficient evidence frcm animal studies. ° The EPA Carcinogen Assessment Group estimated a one-hit slope of 0.1428/tng/kg/day based on the Innes et al. (1969) study identifying male mouse liver tumors as the sensitive sex/species end point (U.S. EPA, 1979). An assumed consumption of 2 liters of water per day by a 70-kg adult over a lifetime results in drinking water concen- trations of 4, 2.4 and 0.24 ug/L for 10~4, 10"* ancj io~6 cancer risk levels, respectively. 0 Data are not available to estimate excess cancer risks using other mathematical models. VI. OTHER CRITERIA, GUIDANCE AND STANDARDS 0 No other data have been located for ETU. VII. ANALYTICAL METHODS 0 Ethylene thiourea is analyzed by a nitrogen-phosphorus detector/qas chromatographic method as described in Method #6 (U.S. EPA, 1988). In this procedure the ETU sample is mixed with ammonium chloride and potassium fluoride and passed through an exchange column (Extrelut). Ihe ETU is then eluted with methylene chloride, concentrated for exchange with ethyl acetate to a volume of 5 mL. The method describes conditions vrtiich permit the separation and measurement of ETU by GC with a nitrogen-phosphorus detector. This method has been validated by a single laboratory. The estimated detection limit for ETU by Method #6 is 5 ug/L. VIII. TREATMENT TECHNOLOGIES 0 No data were found on the removal of ethylene thiourea frcm drinking water by conventional treatment. 0 No data were found on the removal of ethylene thiourea frcm drinkinq water by activated carbon adsorption. However, since ethylene thiourea has a high solubility and is hydrophilic, treatment with activated carbon probably would not be effective. 0 No data were found on the removal of ethylene thiourea frcm drinkinq water by ion exchange. However, the structure of ethylene thiourea indicates it is not ionic and thus probably would not be amenable to ion exchange. ° No data were found on the removal of ethylene thiourea frcm drinking water by aeration. Since vapor pressure data are unavailable, Henry's ------- Ethylene Thiourea August, 1988 -16- Coefficient, and thus the effectiveness of aeration, cannot be estimated. However, the high melting point and the high solubility indicate that Henry's Coefficient would be low and that aeration or air stripping probably would not be an effective form of treatment. ------- Ethylene Thiourea -17- August, 1988 REFERENCES Allen, J.R., J.P. \fon Miller and J.L. Seymour. 1978. Absorption, tissue distribution and excretion of ethylenethiourea by the Rhesus monkey and rat. Res. Conm. Chem. E&th. Iharmacol. 20:109-115. Arnold, D.L., D.R. Krewski, D.B. Junkins , P.F. McGuire, C.A. Moodie and I.C. Munro. 1983. Reversibility of ethylenethiourea-induced thyroid lesions. Toxicol. Appl. Riarmacol. 67:264-273. CHEMLAB. 1985. Ihe Chemical Information System, CIS, Inc. Baltimore, MD. Chernoff, N., R.J. Kavlock, E.H. Rogers, B.D. Carver and S. Murray. 1979. Rsrinatal toxicity of Maneb, ethylene thiourea, and ethylenebisthio- cyanate sulfide in rodents. J. Toxicol. Environ. Health. 5:821-834. Freudenthal, R.I., G. Kerchner, R. Etersing and R. Baron. 1977. Dietary subacute toxicity of ethylene thiourea in the laboratory rat. J. Fnv. Ifeth. Toxicol. 1:147-161. Graham, S.L. and W.H. Hansen. 1972. Effects of short-term administration of ethylene thiourea upon thyroid function of the rat. Bull. Environ. Gontam. Toxicol. 7(1):19-25. Graham, S.L., W.H. Hansen, K.J. Davis and'C.H. Barry. 1973. Effects of one-year administration of ethylenethiourea upon the thyroid of the rat. J. Agr. Food Chem. 21:324-329. Graham, S.L., K.J. E&vis, W.H. Hansen and C.H. Graham. 1975. Effects of prolonged ethylene thiourea ingestion on the thyroid of the rat. Food Gosmet. Toxicol. 13:493-499. Inrtes, J.R., B.M. Ulland, M.G. \felerio, L. Bstrucelli, L. Fishbein, E.R. Hart and A.J. I&llotta. 1969. Bioassay of pesticides and industrial chemicals for tumorigenicity in mice: A preliminary note. J. Natl. Cancer Inst. 42:1101-1114. Iverson, F., K.S. Riera and S.L. Hierlihy. 1980. In vivo and in vitro metabolism of ethylene thiourea in the rat and the cat. Toxicol. Appl. Eharmacol. 52:16-21. Jordan, L.W., and R.A. Neal. 1979. Examination of the in vivo metabolism of maneb and zineb to ethylenethiorea (ETU) in mice. Bull. Environ. Contan. Toxicol. 22:271-277. Khera, K.S. 1973. Ethylene thiourea: teratogenicity study in rats and rabbits. Teratology. 7:243-252. Khera, K.S. 1982. Reduction of teratogenic effects of ethylenethiourea in rats by interaction with sodium nitrite in vivo. Food Cosmet. Toxicol. 20:273-278. ------- Ethylene Thiourea -18- August, 1988 Khera, K.S. 1984. Ethylenethiourea-induced hindpaw deformities in mice and effects of metabolic modifiers on their occurrence. J. Toxicol. Environ. Health. 13:747-756. Khera, K.S., and F. Iverson. 1978. Toxicity of ethylenethiourea in pregnant cats. Teratology. 18:311-314. Wiera, K.S., and L. Tryphonas. 1985. Nerve cell degeneration and progeny survival following ethylenethiourea treatment during pregnancy in rats. Neurol. Toxicol. 6:97-102. Lehman, A.J. 1959. Appraisal of the safety of chemicals in foods, druqs and pesticides. Published in the Assoc. of Food and Drug Officals of the U.S. Meister, R., ed. 1983. Farm chemicals handbook. Willoughby, OH: Meister Publishing Co. Nelson, S.S. 1987. Bioconversion of mancozeb to ETU in rats. Rohm and Haas Technical Report No. 31C-87-24. Submitted to EPA. MRID 40301101. Plasterer, M.R., W.S. Bradshaw, G.M. Booth, M.W. Carter, R.L. Schuler and B.D. Hardin. 1985. Developmental toxicity of nine selected compounds following prenatal exposure in the mouse: Naphthalene, p-nitrophenol, sodium selenite, dimethyl phthalate, ethylenethiourea, and four glycol ether derivatives. J. Toxicol. Ehviron. Health. 15:25-38. Ruddick, J.A. and K.S. Wiera. 1975. Ifettern of anomalies following single oral doses of ethylenethiourea to pregnant rats. Teratology. 12:277-282. Sato, K., N. Nakagata, C.F. Hung, M. Vfeda, T. Shimoji and S. Ishii. 1985. Transplacental induction of myeloschisis associated with hindbrain crowding and other malformations in the central nervous system in Long- Evans rats. Oiild. Nerv. Syst. 1:137-144. Schupbach, M. and H. Hummler. 1977. A comparative study on the mutagenicity of ethylenethiourea in bacterial and mammalian test systems. Mit. Res. 56:111-120. Seiler, J.P. 1973. Ethylenethiourea (ETU), a carcinogenic and mutaqenic metabolite of ethylenebis-dithiocarbamate. Hit. Res. 26:189-191. STORET. 1988. STORET Vfeter Quality File. Office of Vfeter. U.S. Environ- mental Protection Agency (data file search conducted in May, 1988). Teranoto, S., R. Saito and Y. Shirasu. 1980. Teratogenic effects of combined administration of ethylenethiourea and nitrite in mice. Teratology. 21:71-78. Ulland, B.M., J.H. Wteisburger, E.K. Wsisburger, J.M. Rice and R. Cypher. 1972. Brief carmunication: Ihyroid cancer in rats from ethylene thiourea intake J. Natl. Cancer Inst. 49:583-584. ------- Ethylene Thiourea August, 1988 -19- U.S. EPA. 1979. U.S. Environmental Rrotection Agency. Ihe Carcinogen Assessment Group's Risk Assessment on Ethylene Bisdithiocarbamate. U.S. EPA. 1982. U.S. Environmental Protection Agency. Ethylene Bisdithio- carbamate Pesticides. Etecision Ebcument. Final Resolution of Rebuttable Presumption Against Registration. Office of Pesticide Programs. U.S. EPA. 1986a. U.S. Environmental Protection Aqency. Final report. Task 2: Envirorroental Fate and Exposure Assessment. June 10. U.S. EPA. 1986b. U.S. Environmental Protection Aqency. Guidelines for carcinogen risk assessment. Fed. Reg. 51(185):33992-34003. September 24. U.S. EPA. 1988. U.S. Environmental Protection Agency. Method #6 - Determi- nation of Ethylene Thiourea (ETU) in Ground v&ter by Gas Chromatography with a Nitrogen-FhosDhorus Detector. Available fran U.S. EPA's Environ- mental Monitoring and Support laboratory, Cincinnati, OH 45268. Windholz, M., S. Budavari, R.F. Blumetti and E.S. Otterbein, eds. 1983. The Merck Index, 10th ed. Rah way, N.J.: Merck and Co., Inc. ------- |