United States Environmental Protection 1=1 m m Agency EPA/690/R-07/018F Final 9-11-2007 Provisional Peer Reviewed Toxicity Values for Gadolinium (CASRN 7440-54-2) Superfund Health Risk Technical Support Center National Center for Environmental Assessment Office of Research and Development U.S. Environmental Protection Agency Cincinnati, OH 45268 ------- Acronyms and Abbreviations bw body weight cc cubic centimeters CD Caesarean Delivered CERCLA Comprehensive Environmental Response, Compensation and Liability Act of 1980 CNS central nervous system cu.m cubic meter DWEL Drinking Water Equivalent Level FEL frank-effect level FIFRA Federal Insecticide, Fungicide, and Rodenticide Act g grams GI gastrointestinal HEC human equivalent concentration Hgb hemoglobin i.m. intramuscular i.p. intraperitoneal IRIS Integrated Risk Information System IUR inhalation unit risk i.v. intravenous kg kilogram L liter LEL lowest-effect level LOAEL lowest-observed-adverse-effect level LOAEL(ADJ) LOAEL adjusted to continuous exposure duration LOAEL(HEC) LOAEL adjusted for dosimetric differences across species to a human m meter MCL maximum contaminant level MCLG maximum contaminant level goal MF modifying factor mg milligram mg/kg milligrams per kilogram mg/L milligrams per liter MRL minimal risk level MTD maximum tolerated dose MTL median threshold limit NAAQS National Ambient Air Quality Standards NOAEL no-ob served-adverse-effect level NOAEL(ADJ) NOAEL adjusted to continuous exposure duration NOAEL(HEC) NOAEL adjusted for dosimetric differences across species to a human NOEL no-ob served-effect level OSF oral slope factor p-IUR provisional inhalation unit risk p-OSF provisional oral slope factor p-RfC provisional inhalation reference concentration p-RfD provisional oral reference dose 1 ------- PBPK physiologically based pharmacokinetic ppb parts per billion ppm parts per million PPRTV Provisional Peer Reviewed Toxicity Value RBC red blood cell(s) RCRA Resource Conservation and Recovery Act RDDR Regional deposited dose ratio (for the indicated lung region) REL relative exposure level RfC inhalation reference concentration RfD oral reference dose RGDR Regional gas dose ratio (for the indicated lung region) s.c. subcutaneous SCE sister chromatid exchange SDWA Safe Drinking Water Act sq.cm. square centimeters TSCA Toxic Substances Control Act UF uncertainty factor Hg microgram |j,mol micromoles voc volatile organic compound 11 ------- 9-11-2007 PROVISIONAL PEER REVIEWED TOXICITY VALUES FOR GADOLINIUM (CASRN 7440-54-2) Background On December 5, 2003, the U.S. Environmental Protection Agency's (EPA's) Office of Superfund Remediation and Technology Innovation (OSRTI) revised its hierarchy of human health toxicity values for Superfund risk assessments, establishing the following three tiers as the new hierarchy: 1. EPA's Integrated Risk Information System (IRIS). 2. Provisional Peer-Reviewed Toxicity Values (PPRTV) used in EPA's Superfund Program. 3. Other (peer-reviewed) toxicity values, including: ~ Minimal Risk Levels produced by the Agency for Toxic Substances and Disease Registry (ATSDR), ~ California Environmental Protection Agency (CalEPA) values, and ~ EPA Health Effects Assessment Summary Table (HEAST) values. A PPRTV is defined as a toxicity value derived for use in the Superfund Program when such a value is not available in EPA's Integrated Risk Information System (IRIS). PPRTVs are developed according to a Standard Operating Procedure (SOP) and are derived after a review of the relevant scientific literature using the same methods, sources of data, and Agency guidance for value derivation generally used by the EPA IRIS Program. All provisional toxicity values receive internal review by two EPA scientists and external peer review by three independently selected scientific experts. PPRTVs differ from IRIS values in that PPRTVs do not receive the multi-program consensus review provided for IRIS values. This is because IRIS values are generally intended to be used in all EPA programs, while PPRTVs are developed specifically for the Superfund Program. Because new information becomes available and scientific methods improve over time, PPRTVs are reviewed on a five-year basis and updated into the active database. Once an IRIS value for a specific chemical becomes available for Agency review, the analogous PPRTV for that same chemical is retired. It should also be noted that some PPRTV manuscripts conclude that a PPRTV cannot be derived based on inadequate data. Disclaimers Users of this document should first check to see if any IRIS values exist for the chemical of concern before proceeding to use a PPRTV. If no IRIS value is available, staff in the regional Superfund and RCRA program offices are advised to carefully review the information provided in this document to ensure that the PPRTVs used are appropriate for the types of exposures and circumstances at the Superfund site or RCRA facility in question. PPRTVs are periodically updated; therefore, users should ensure that the values contained in the PPRTV are current at the time of use. 1 ------- 9-11-2007 It is important to remember that a provisional value alone tells very little about the adverse effects of a chemical or the quality of evidence on which the value is based. Therefore, users are strongly encouraged to read the entire PPRTV manuscript and understand the strengths and limitations of the derived provisional values. PPRTVs are developed by the EPA Office of Research and Development's National Center for Environmental Assessment, Superfund Health Risk Technical Support Center for OSRTI. Other EPA programs or external parties who may choose of their own initiative to use these PPRTVs are advised that Superfund resources will not generally be used to respond to challenges of PPRTVs used in a context outside of the Superfund Program. Questions Regarding PPRTVs Questions regarding the contents of the PPRTVs and their appropriate use (e.g., on chemicals not covered, or whether chemicals have pending IRIS toxicity values) may be directed to the EPA Office of Research and Development's National Center for Environmental Assessment, Superfund Health Risk Technical Support Center (513-569-7300), or OSRTI. This document has passed the STSC quality review and peer review evaluation indicating that the quality is consistent with the SOPs and standards of the STSC and is suitable for use by registered users of the PPRTV system. INTRODUCTION Stable (nonradioactive) gadolinium is the subject of this issue paper. No toxicity or carcinogenicity assessments of gadolinium are available from IRIS (U.S. EPA, 2007a), HEAST (U.S. EPA, 1997), or the Office of Water (U.S. EPA, 2007b). Gadolinium has not been evaluated by ATSDR (2007) or IARC (2007), or tested or scheduled for testing by NTP (2007). No occupational exposure limits are recommended or promulgated for gadolinium by ACGIH (2007), NIOSH (2007), or OSHA (1989, 1993). This issue paper is based on information obtained through comprehensive searches of the following databases in 2007: TOXLINE (1965-2007), CANCERLINE (1970-2007), MEDLINE (1966-2007), GENETOX, DART, CCRIS, CHEMID, RTECS, EMIC, ETICBACK, and TSCATS. Extensive tree-searching of acquired literature was performed to identify pertinent data from the older literature. REVIEW OF PERTINENT LITERATURE Human Studies No human studies were located regarding exposure of humans to gadolinium. 2 ------- 9-11-2007 Animal Studies Oral Toxicity Data Groups of 6 male and 6 female rats (strain not reported) were fed 0, 0.01,0.1, or 1% dietary gadolinium chloride (98% pure) for 12 weeks (Haley et al., 1961). Compound intake is estimated to be 9.1, 91, or 935 mg/kg-day (5.4, 54, or 558 mg Gd/kg-day) in the males, and 10.0, 100, or 1001 mg/kg-day (6.0, 60, or 597 mg Gd/kg-day) in the females. These intake values were calculated using reported body weight data (from growth curves) data, and food consumption estimates based on an allometric equation relating food consumption to body weight (U.S. EPA, 1988). Body weight was measured biweekly throughout the study, and hematology (total erythrocytes, total leucocytes, differential cell count, hemoglobin, and hematocrit) and histology (heart, lung, liver, kidney, pancreas, spleen, adrenal, and small intestine) were assessed at the end of the study. Exposure-related changes in liver histology were observed in the males at 558 mg Gd/kg-day. The liver effects consisted of perinuclear vacuolization and coarse granular cytoplasm in parenchymal cells in 6/6 of the high-dose males; these effects were "not regularly observed" in the lower dose male groups (incidence data not reported) and were absent in females. Liver pathology findings in controls were not reported but incidences are presumed to be 0/6 in each sex. Although the liver pathology findings suggest adverse effects at the high dose in males, the data are insufficient to clearly discern the threshold. A 10% reduction in body weight gain in males exposed to the highest dose (558 mg Gd/kg-day), reported in the earlier PPRTV draft, could not be verified because Figure 1 in the Haley et al. (1961) study clearly shows that the lower body weight was associated with the lowest dose (5.4 mg Gd/kg-day). The male rat body weights at the two higher doses were indistinguishable from the control weights. Nothing in the study text helps determine whether the Figure 1 legend contains a typographical error or which dose caused the effect. Assessment of the body weight data is further complicated by the lack of a dose-response and by a magnitude (-10% decreased weight gain) that is imprecise due to estimation from growth curves and not unequivocally adverse. Assessment of the liver pathology data is complicated by the small group sizes, unreported incidences in the control, low- and mid-dose groups, and possible adverse effects in the low- and mid-dose groups as indicated by observations of liver lesions in some of the animals. These insufficiencies in the body weight and liver pathology data preclude clearly identifying a NOAEL and LOAEL from this study. Inhalation Toxicity Data CFW mice were exposed to 0 or ~ 30 mg/m3 concentrations of gadolinium oxide (Gd2C>3) aerosol (99.9% pure, mean particle diameter 0.312ja, 17.9 mg Gd/m3) for 6 hours/day, 5 days/week for 20, 40, 60, 80, 100 or 120 days, and observed for duration of natural life (Ball and VanGelder, 1966). The numbers of animals in the control and exposed groups ranged from 6-10 and 20-30, respectively, and were equally divided by sex. Hematology (total and differential leukocyte counts, hemoglobin levels, packed cell volume, and clotting times) was assessed in 20%) of the surviving mice at the end of each exposure period and at 12 and 18 months after the start of the study. Following natural death all animals were necropsied and histologically examined (unspecified representative tissues). Average lifespan ranged from 7.8-19.7 and 9.2- 13.3 months in the groups of control and exposed mice, respectively. Mortality from pneumonia 3 ------- 9-11-2007 was increased in most groups of exposed groups of mice but not related to duration of exposure; the overall average mortality in the exposed mice was 22% compared to 14% in controls. Most of the pneumonia-related mortality occurred 2-5 weeks after exposure started. Calcification in the lung occurred in 32-95%) of the groups of exposed mice, but in none of the controls; the overall average percentage of mice with pulmonary calcification was 54.8%. The incidences of pulmonary calcification were not clearly related to duration of exposure. Fibrosis was noted rarely in the lungs of the mice exposed for shorter durations and occasionally observed in the 120-day exposure group; incidences of fibrosis were not reported. The severity of the lung pathology and consequent mortality indicates that 17.9 mg Gd/m3 was a frank effect level (FEL) in mice. Pulmonary toxicity was evaluated in groups of 6 male and 6 female guinea pigs who were exposed to Gd203 aerosol in concentrations of 0 or 20 mg/m3 (11.9 mg Gd/m3) for 6 hours/day, 5 days/week for 40, 80, or 120 days (Abel and Talbot, 1967). Most (92%) of the particles were <0.563[j, in diameter. Pulmonary function (elasticity determined by compliance measurements on excised lungs) and lung histology were assessed at the end of the exposure periods. A highly significant (p<0.01) linear trend in the exposed groups indicated that lung elasticity decreased with increasing duration of exposure. Histopathologic changes in the exposed lungs became more severe as exposure time increased and included alveolar cell hypertrophy, septal cell wall thickening, nodular lymphoid hyperplasia, and macrophage proliferation. These pulmonary effects indicate that 11.9 mg Gd/m3 was a LOAEL in guinea Pigs- Other Studies Measurements of excreta and carcass showed that gastrointestinal absorption of gadolinium as a Gd159-citrate complex was <0.1% in 4 days following an unspecified gavage dose in rats (Durbin et al., 1956). An oral LD50 value of >1743 mg Gd/kg was determined for gadolinium nitrate in female rats that were observed for 30 days following administration (Bruce et al., 1963). Acute intraperitoneal LD50s of 80 mg Gd/kg for gadolinium nitrate in female rats observed for 30 days, 105 mg Gd/kg for gadolinium nitrate in female mice observed for 30 days, and 328 mg Gd/kg for gadolinium chloride in male mice observed for 7 days have also been determined (Bruce et al., 1963; Haley et al., 1961). Symptoms of acute gadolinium chloride toxicity in the mice included decreased respiration, lethargy, abdominal cramps, and diarrhea (Haley et al., 1961). Gadolinium has strong paramagnetic properties that are used as the basis of intravenous magnetic resonance imaging agents (Cacheris et al., 1990; Mann, 1993). These compounds are stable chelates in which the gadolinium cation is incorporated in polybasic organic ligands, often polyaminocarboxylate molecules derived from the parent molecule EDTA. The intravenous use of gadolinium in chelated form is necessary to reduce Gd+3 toxicity and improve its solubility (free gadolinium ion is readily precipitated in vivo), tissue distribution (precipitates are deposited in liver, bone, and other tissues), and renal clearance. A number of gadolinium-chelate complexes have been developed and tested for clinical safety, including gadopentetate dimeglumine, gadodiamide, gadoterate meglumine, and gadoteridol. 4 ------- 9-11-2007 Groups of 4 male Wistar rats were administered doses of 0, 10, 20, 50, or 100 jag Gd/rat (approximately 0.04, 0.08, 0.2, or 0.4 mg Gd/kg, based on reported body weight data) as gadolinium chloride by intratracheal instillation and killed after 2 days (Yoneda et al., 1995). Other groups of 4 rats were similarly treated with 50 jag Gd/rat and killed at intervals ranging from 0 hours to 175 days following instillation. There was a dose-related deposition of insoluble forms of Gd in the lung tissue where the content decreased slowly with a calculated biological half-life of 136 days (for the 0.2 mg Gd/kg dose); 26% of the initial dose remained in the lung tissue 175 days after exposure. The Gd content in the bronchoalveolar lavage fluid remained at a constant level (about 5 |ig) over the 0.08-0.4 mg Gd/kg dose range and was not detectable after 31 days. The pulmonary toxicity of inhaled rare earth compounds, in general, have been the subject of debate, especially with regard to the relative contributions of radioactive contaminants versus stable elements in the development of progressive pulmonary interstitial fibrosis (Haley, 1991; Beliles, 1994). In particular, although it is known that stable rare earth compounds can produce a static, foreign-body-type lesion consistent with benign pneumoconiosis, there is uncertainty whether they can also induce interstitial fibrosis that progresses after termination of exposure. Human inhalation toxicity data on stable rare earth elements mainly consist of case reports on workers exposed to multiple lanthanides (Kappenberger and Buhlmann, 1975; Husain et al., 1980; Sabbioni et al., 1982; Vocaturo et al., 1983; Colombo et al., 1983; Sulotto et al., 1986; Vogt et al., 1986; Waring and Watling, 1990; Deng et al., 1991). Animal inhalation toxicity data on stable rare earths mainly consist of a few inhalation or intratracheal studies on some rare earth mixtures and some single compounds (Schepers, 1955a,b; Schepers et al., 1955; Ball and VanGelder, 1966; Abel and Talbot, 1967; Mogilevskaya and Raikhlin, 1967). A comprehensive assessment of the human and animal data by Haley (1991) concluded that the evidence suggests that inhalation exposure to high concentrations of stable rare earths can produce lesions compatible with pneumoconiosis and progressive pulmonary fibrosis, and that the potential for inducing these lesions is related to chemical type, physiochemical form, and dose and duration of exposure. Carcinogenicity Data No oral carcinogenicity studies of gadolinium were located in the available literature. A 90-day feeding study of gadolinium chloride was performed in rats (Haley et al., 1961), but it is inadequate for assessing carcinogenic effects due to insufficient duration of exposure and lack of a posttreatment observation period. An inhalation study was performed in which groups of CFW mice were exposed to 0 or ~ 30 mg/m3 conentration of gadolinium oxide aerosol (99.9% pure, mean particle diameter 0.312[j,, 17.9 mg Gd/m3) for 6 hours/day, 5 days/week for up to 120 days, and observed for life (Ball and VanGelder, 1966). The numbers of animals in the control and exposed groups ranged from 6-10 and 20-30, respectively. Incidences of primary lung tumors were not increased in the exposed mice although nonneoplastic lesions occurred in the lungs (see summary in RfC Assessment). Tumor incidences in tissues other than lung were not reported or discussed. 5 ------- 9-11-2007 An implantation study was performed in which groups of 30 male and 30 female weanling CFW mice were subcutaneously administered a 200 mg pellet of gadolinium (1.5-2.0 mm diameter) and observed for life (Ball et al., 1970). Comparison with 16 male and 16 female sham-implanted controls showed no clear treatment-related induction of local sarcomas. Incidences of implantation-sited sarcomas were 1/30 and 0/16 in treated and control males, respectively, and 2/30 and 0/16 in treated and control females, respectively. No tumor metastases were observed. Implantation-site granulomas that were indicative of a foreign-body reaction developed in treated mice (15/30 males, 18/30 females) but not in controls. Supporting Data Genotoxicity and other supportive data relating to the potential carcinogenicity of stable gadolinium were not located in the available literature. DERIVATION OF A PROVISIONAL SUBCHRONIC OR CHRONIC RfD FOR GADOLINIUM Information on the toxicity of repeated oral exposure to gadolinium is limited to a 12- week dietary study which found minimally decreased body weight gain and liver histological alterations in male, but not female, rats (Haley et al., 1961). Inadequacies in study design and reporting, particularly small group sizes and incomplete incidence data, preclude clearly establishing NOAELs and LOAELs and possible derivation of an RfD. DERIVATION OF A PROVISIONAL SUBCHRONIC OR CHRONIC RfC FOR GADOLINIUM Limited information is available on the toxicity of repeated inhalation exposures to gadolinium. Subchronic studies were performed in which mice and guinea pigs were intermittently exposed to single dose levels of gadolinium oxide for up to 3 months and, in the case of the mice, subsequently observed for life (Ball and VanGelder, 1966; Abel and Talbot, 1967). Marked pulmonary histopathological changes occurred in both studies with manifestations that included decreased lung compliance and pneumonia leading to mortality. Although the findings in these animal studies appear to be consistent with pulmonary effects of inhalation exposure to high concentrations of rare earth compounds in general, the single dose levels showing a LOAEL or FEL preclude discerning the exposure-response threshold and possible derivation of an RfC. PROVISIONAL CARCINOGENICITY ASSESSMENT FOR GADOLINIUM Weight-of-Evidence Classification Carcinogenicity data on gadolinium are essentially limited to two studies. Lung tumors were not induced in mice that were observed for life following subchronic inhalation of a 6 ------- 9-11-2007 pulmonary toxic concentration (single exposure level) of gadolinium oxide (Ball and Van Gelder, 1966), and subcutaneous implantation of a gadolinium pellet caused no clear treatment- related induction of local sarcomas or metastases in mice observed for life (Ball et al., 1970). The lack of additional studies precludes assessing possible carcinogenicity. In accordance with U.S. EPA (2005) guidelines for chemicals with inadequate human and animal data, stable gadolinium is assigned a weight-of-evidence (WOE) description of "inadequate information to assess carcinogenic potential." Consequently the human carcinogenicity of gadolinium cannot be determined. Quantitative Estimates of Carcinogenic Risk Derivation of an oral slope factor or inhalation unit risk for stable gadolinium is precluded by the lack of adequate studies in humans and animals. REFERENCES Abel, M. and R.B. Talbot. 1967. Gadolinium oxide inhalation by guinea pigs: A correlative functional and histopathologic study. J. Pharmacol Exp. Therap. 157: 207-213. ACGIH (American Conference of Governmental Industrial Hygienists). 2007. TLVs and BEIs. Threshold Limit Values for Chemical Substances and Physical Agents and Biological Exposure Indices. ACGIH, Cincinnati, OH. ATSDR (Agency for Toxic Substances and Disease Registry). 2007. Internet HazDat Database: Toxicological Profile Query. (Http://atsdrl.atsdr.cdc.gov:8080/gsql/toxprof.script). ATSDR, U.S. Public Health Service, Atlanta, GA. Ball, R.A. and G. VanGelder. 1966. Chronic toxicity of gadolinium oxide for mice following exposure by inhalation. Arch. Environ. Health. 13: 601-608. Ball, R.A., G. VanGelder, J.W. Green Jr. and W.O. Reece. 1970. Neoplastic sequelae following subcutaneous implantation of mice with rare earth metals. Proc. Soc. Exp. Med. 135: 426-430. Beliles, R.P. 1994. The Lanthanides. In: Patty's Industrial Hygiene and Toxicology, Fourth Edition, Volume 2, Part C. Edited by G.D. Clayton and F.E. Clayton. John Wiley and Sons, Inc., New York, NY. pp. 2048-2065. Bruce, D.W, B.E. Hietbrink and K.P. DuBois. 1963. The acute mammalian toxicity of rare earth nitrates and oxides. Toxicol. Appl. Pharmacol. 5:750-759. Cacheris, W.P., S.C. Quay and S.M. Rocklage. 1990. The relationship between thermodynamics and the toxicity of gadolinium complexes. 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Aust. 153: 726-730. Yoneda, S., N. Emi, Y. Fujita, M. Ohmichi, S. Hirano and K.T. Suzuki. 1995. Effects of gadolinium chloride on the rat lung following intratracheal instillation. Fund. App. Toxicol. 28: 65-70. 10 ------- |