United Slates Environmental Protection Aqency Off'ce of Water Regulations and Standards. Washington, DC 20460 Water June, 1989 lethylene bis(2-chloroaniline' *y * ------- PREFACE This document is one of a series of preliminary assessments dealing with chemicals of potential concern in municipal sewage sludge. The purpose of these documents is to: (a) summarize the available data for the constituents of potential concern, (b) identify the key environ- mental pathways for each constituent related to a reuse and disposal option (based on hazard indices), and (c) evaluate the conditions under which such a pollutant may pose a hazard. Each document provides a sci- entific basis for making an initial determination of whether a pollu- tant, at levels currently observed in sludges, poses a likely hazard to human health or the environment when sludge is disposed of by any of several methods. These methods include landspreading on food chain or nonfood chain crops, distribution and marketing programs, landfilling, incineration and ocean disposal. These documents are intended to serve as a rapid screening tool to narrow an initial list of pollutants to those of concern. If a signifi- cant hazard is indicated by this preliminary analysis, a more detailed assessment will be undertaken to better quantify the risk from this chemical and to derive criteria if warranted. If a hazard is shown to be unlikely, no further assessment will be conducted at this time; how- ever, a reassessment will be conducted after initial regulations are finalized. In no case, however, will criteria be derived solely on the basis of information presented in this document. ------- TABLE OF CONTENTS Page PREFACE i 1. INTRODUCTION. 1-1 2. PRELIMINARY CONCLUSIONS FOR 4,4'-METHYLENE BIS (2-CHLOROANILINE) IN MUNICIPAL SEWAGE SLUDGE 2-1 Landspreading and Distribution-and-Marketing 2-1 Landfilling 2-2 Incineration - 2-2 Ocean Disposal 2-2 3. PRELIMINARY HAZARD INDICES FOR 4,4'-METHYLENE BIS (2-CHLOROANILINE) IN MUNICIPAL SEWAGE SLUDGE 3-1 Landspreading and Distribution-and-Marketing 3-1 Effect on soil concentration of 4,4'-Methylene Bis (2-ChloroaniLine) (Index 1) ; . . . 3-1 Effect on soil biota and predators of soil biota (Indices 2-3) 3-3 Effect on plants and plant tissue concentration (Indices 4-6) 3-4 Effect on herbivorous animals (Indices 7-8) 3-7 Effect on humans (Indices 9-13) 3-10 Landf illing ' 3-16 Incineration 3-16 Ocean Disposal 3-16 4. PRELIMINARY DATA PROFILE FOR 4,4'-METHYLENE BIS (2-CHLOROANILINE) IN MUNICIPAL SEWAGE SLUDGE 4-1 Occurrence 4-1 Sludge 4-1 Soil - Unpolluted 4-1 Water - Unpolluted 4-2 Air 4-2 Food 4-3 ------- TABLE OF CONTENTS (Continued) Page Human Effects 4-3 Ingestion 4-3 Inhalation 4-4 Plant Effects 4-5 Phytotoxicity 4-5 Uptake 4-5 Domestic Animal and Wildlife Effects 4-5 Toxicity 4-5 Uptake 4-5 Aquatic Life Effects • 4-5 Soil Biota Effects 4-5 Physicochemical Data for Estimating Fate and Transport 4-5 5 . REFERENCES ". 5-1 APPENDIX. PRELIMINARY HAZARD INDEX CALCULATIONS FOR 4,4'-METHYLENE BIS (2-CHLOROANILINE) IN MUNICIPAL SEWAGE SLUDGE A-l 111 ------- SECTION 1 INTRODUCTION This preliminary data profile is one of a series of profiles dealing with chemical pollutants potentially of concern in municipal sewage . sludges. 4,4'-Methylene bis (2-chloroahiline) (MOCA)' was ini- tially identified as being of potential concern when sludge is land- spread (including distribution-and-marketing).* This profile is a com- pilation of information that may be useful in determining whether MOCA poses an actual hazard to human health or the environment when sludge is disposed of by this method. The focus of this document is the calculation of "preliminary hazard indices" for selected potential exposure pathways, as shown in Section 3. Each index illustrates the hazard that could result from movement of a pollutant by a given pathway to cause a given effect (e.g., sludge •* soil •* plant uptake •*• animal uptake •* human toxicity). The values and assumptions employed in these calculations tend to repre- sent a reasonable "worst case"; analysis of error or uncertainty has been conducted to a limited degree. The resulting value in most cases is indexed to unity; i.e., values >1 may indicate a potential hazard, depending upon the assumptions of the calculation. The data used for index calculation have been selected or estimated based on information presented in the "preliminary data profile", Sec- tion 4. Information in the profile is based on a compilation of the recent literature. An attempt has been, made to fill out the profile outline to the greatest extent possible. However, since this is a pre- liminary analysis, the literature has not been exhaustively perused. The "preliminary conclusions" drawn from each index in Section 3 are summarized in Section 2. The preliminary hazard indices will be used as a screening tool to determine which pollutants and pathways may pose a hazard. Where a potential hazard is indicated by interpretation of these indices, further analysis will include a more detailed exami- nation of potential risks as well as an examination of site-specific factors. These more rigorous evaluations may change the preliminary conclusions presented in Section 2, which are based on a reasonable "worst case" analysis. The preliminary hazard indices for selected exposure routes pertinent to landspreading and distribution and marketing are included in this profile. The calculation formulae for these indices are shown in the Appendix. The indices are rounded to two significant figures. * Listings were determined by a series of expert workshops convened during March-May, 1984 by the Office of Water Regulations and Standards (OWRS) to discuss landspreading, landfilling, incineration, and ocean disposal, respectively, of municipal sewage sludge. 1-1 ------- SECTION 2 PRELIMINARY CONCLUSIONS FOR 4,4'-METHYLENE BIS (2-CHLOROANILINE) IN MUNICIPAL SEWAGE SLUDGE The following preliminary conclusions have been derived from the calculation of "preliminary hazard indices", which represent conserva- tive or "worst case" analyses of hazard. The indices and their basis and interpretation are explained in Section 3. - Their calculation formulae are shown in the Appendix. I. LANDSPREADING AND DISTRIBUTION-AND-MARKETING A. Effect on Soil Concentration of 4,4-Methylene Bis (2-Chloroani1ine) Soil concentrations of MOCA are expected to increase slightly with 5 to 50 mt/ha application rates of municipal sewage sludge. Long term applications of sewage sludge are expected to result in moderate increases of MOCA concentrations in the amended soils (see Index 1). B. Effect on Soil Biota or Predators of Soil Biota Conclusions were not drawn about the effect of MOCA on soil biota and predators because index values could not be calcu- lated due to lack of immediately available data (see Indices 2 and 3). C. Effect on Plants and Plant Tissue Concentration Conclusions were not able"to be drawn concerning the effects of MOCA on plants (see Index 4); however, the application of municipal sewage sludge to soil is not expected to result in increased concentrations of MOCA in plant tissue grown on the amended soils (see Index 5). Phytotoxic levels were also not able to be determined due to a lack of data (see Index 6). D. Effect on Herbivorous Animals The consumption of plant tissue grown on sludge-amended soils by herbivorous animals is not expected to pose a toxic hazard due to MOCA ingestion (see Index 7). Also, the consumption of crops to which sludge-amended soil or sludge adheres is not expected to pose a MOCA hazard to herbivorous animals (see Index 8). E. Effect on Humans Conclusions could not be drawn about the potential effect of MOCA on humans because index values could not be calculated due to lack of immediately available data (see Indices 9 to 13). 2-1 ------- II. LANDPILLING Based on che recommendations of the experts at the OWRS meetings (April-May, 1984), an assessment of this reuse/disposal option is not being conducted at this time. The U.S. EPA reserves the right to conduct such an assessment for this option in the future. III. INCINERATION Based on the recommendations of the experts at the OWRS meetings (April-May, 1984), an assessment of this reuse/disposal option is not being conducted at this time. The U.S. EPA reserves the right to conduct such an assessment for this option in the future. IV. OCEAN DISPOSAL Based on the recommendations of the experts at the OWRS meetings (April-May, 1984), an assessment of this reuse/disposal option is not being conducted at this time. The U.S. EPA reserves the right to conduct such an assessment for this option in the future. 2-2 ------- SECTION 3 PRELIMINARY HAZARD INDICES FOR 4,4'-METHYLENE BIS (2-CHLOROANILINE) IN MUNICIPAL SEWAGE SLUDGE LANDSPREADING AND DISTRIBUTION-AND-MARKETING A. Effect on Soil Concentration of 4,4'-Methylene Bis (2-Chloroaniline) 1. Index of Soil Concentration (Index 1) a. Explanation - Calculates concentrations in Ug/g DW of pollutant in sludge-amended soil. Calculated for sludges with typical (median, if available) and worst (95 percentile, if available) pollutant concentrations, respectively, for each • of four applications. Loadings (as dry matter) are chosen and explained as follows: 0 mt/ha No sludge applied. Shown for all indices for purposes of comparison, to distin- guish hazard posed by sludge from pre- existing hazard posed by background levels or other sources of the pollutant. 5 mt/ha Sustainable yearly agronomic application; i.e., loading typical of agricultural practice, supplying -^50 kg available nitrogen per hectare. 50 mt/ha Higher single application as may be used on public lands, reclaimed areas or home gardens. 500 mt/ha Cumulative loading after 100 years of application at 5 mt/ha/year. b. Assumptions/Limitations - Assumes pollutant is incorporated into the upper 15 cm of soil (i.e., the plow layer), which has an approximate mass (dry matter) of 2 x 10^ mt/ha and is then dissipated through first order processes which can be expressed as a soil half-life. c. Data Used and Rationale i. Sludge concentration of pollutant (SC) Typical 18.0 Ug/g DW Worst 86.0 Ug/g DW 3-1 ------- Information on sludge concentrations of MOCA is derived primarily from studies of Adrian, Michigan where a MOCA manufacturing plant oper- ated "(U.S. EPA, 1980; Parris et al., 1980). In Adrian, MOCA concentrations in sludge are reported to range between 0.006 Ug/g for "return" sludge to 86.0 Ug/g for sludge from dry beds at the wastewater treatment plant. The value of 18.0 Ug/g (DW) applies to acti- vated sludge. To be conservative, the two highest values of known sludge concentrations of MOCA, 18.0 Ug/g and 86.0 Ug/g, are used for the typical and worst case sludge concentra- tions, respectively. (See Section 4, p. 4-1.) ii. Background concentration of pollutant in soil (BS) = 2.9 Ug/g DW Estimates of the ambient soil concentrations of MOCA have been derived from soil analyses in Adrian, Michigan (U.S. EPA, 1980). Soil levels by roadways vary by distance from the MOCA man- ufacturing plant, being 13 ppm (W/W) at 0.4 mile to 2.1 ppm at over 1 mile from the plant. MOCA levels in garden soils are in the range of 0.08 to 2.9 ppm on the surface, but decline to 0.01 to 0.86 for subsurface garden soils. At two Adrian wastewater treatment plant sites, the soil concentrations of MOCA were 1.6 and 6.5 ppm. The value of 2.9 Ug/g DW was selected as a conservative estimate of the range of reported soil concentrations. (See Section 4, pp. 4-1 and 4-2.) iii. Soil half-life of pollutant (ti) = 5.3 years The half-life of MOCA has been reported to range between 3.69 hours to 12.96 hours for photolysis. 12.96 hours for oxidation, and 1.07 x 10^ hours for volatilization (Versar, 1980). Based on these estimates, an average half-life of 4.667 x 104 hours or 5.3 years has been derived (Versar, 1980). Given the scarcity of data on MOCA, this estimate is used as a reasonable first approximation of the chemical's half-life in soil. It should be noted the underlying assumption of this estimate is that all of the above processes are involved in the decomposition of MOCA. (See Section 4, p. 4-2.) 3-2 ------- d. Index 1 Values (mg/g DW) Sludge Application Rate (mt/ha) Sludge Concentration Typical Worst 0 2.9 2.9 5 2^9 3.1 50 3.3 4.9 500 24 25 e. Value Interpretation - Value equals the expected concentration in sludge-amended soil. f. Preliminary Conclusion - Soil concentrations of MOCA are expected to increase slightly with 5 to 50 mt/ha application rates of municipal sewage sludge. Long- term applications of sewage sludge are expected to result in moderate increases of MOCA concentrations in the amended soils. B. Effect on Soil Biota and Predators of Soil Biota 1. Index of Soil Biota Toxicity (Index 2) a. Explanation - Compares pollutant concentrations in sludge-amended soil with soil concentration shown to be toxic for some soil organism. b. Assumptions/Limitations - Assumes pollutant form in sludge-amended soil is equally bioavailable and toxic as form used in study where toxic effects were demonstrated. c. Data Used and Rationale i. Concentration of pollutant in sludge-amended soil (Index 1) See Section 3, p. 3-3. ii. Soil concentration toxic to soil biota (TB) - Data not immediately available. d. Index 2 Values - Values were not calculated due to lack of data. e. Value Interpretation - Value equals factor by which expected soil concentration exceeds toxic concentra- tion. Value > 1 indicates a toxic hazard may exist for soil biota. 3-3 ------- f. Preliminary Conclusion - Conclusion was not drawn because index values could not be calculated. 2. Index of Soil Biota Predator Toxicity (Index 3) a. Explanation - Compares pollutant concentrations expected in tissues of organisms inhabiting sludge- amended soil with food concentration shown to be toxic to a predator on soil organisms. b. Assumptions/Limitations - Assumes pollutant form bioconcentrated by soil biota is equivalent in toxicity to form used to demonstrate toxic effects in predator. Effect level in predator may be estimated from that in a different species. c. Data Used and Rationale i. Concentration of pollutant in sludge-amended soil (Index 1) See Section 3, p. 3-3. ii. Uptake factor of pollutant in soil biota (UB) - Data not immediately available. iii. Feed concentration toxic to predator (TR) Data not immediately available. d. Index 3 Values - Values were not calculated due to lack of data. e. Value Interpretation - Values equals factor by which expected concentration in soil biota exceeds that which is toxic to predator. Value > 1 indicates a toxic hazard may exist for predators of soil biota. f. Preliminary Conclusion - Conclusion was not drawn because index values could not be calculated. C. Effect on Plants and Plant Tissue Concentration 1. Index of Phytotoxic Soil Concentration (Index 4) a. Explanation - Compares pollutant concentrations in sludge-amended soil with the lowest soil concentration shown to be toxic for some plants. b. Assumptions/Limitations - Assumes pollutant form in sludge-amended soil is equally bioavailable and toxic as form used in study where toxic effects were demonstrated. 3-4 ------- c. Data Used and Rationale i. Concentration of pollutant in sludge-amended soil (Index 1) See Section 3, p. 3-3. ii. Soil concentration toxic to plants (TP) - Data not immediately available. d. Index 4 Values - Values were not calculated due to lack of data. e. Value Interpretation - Value equals factor by which soil concentration exceeds phytotoxic concentration. Value > 1 indicates a phytotoxic hazard may exist. f. Preliminary Conclusion - Conclusion was not drawn because index values could not be calculated. Index of Plant Concentration Caused by Uptake (Index 5) a. Explanation - Calculates expected tissue concentrations, in Ug/g DW, in plants grown in sludge-amended soil, using uptake data for the most responsive plant species in the following categories: (1) plants included in the U.S. human diet; and (2) plants serving as animal feed. Plants used vary according to availability of data. b. Assumptions/Limitations - Assumes an uptake factor that is constant over all soil concentrations. The uptake factor chosen for the human diet is assumed to be representative of all crops (except fruits) in the human diet. The uptake factor chosen for the animal diet is assumed to be representative of all crops in the animal diet. See also Index 6 for consideration of phytotoxicity. c. Data Used and Rationale i. Concentration of pollutant in sludge-amended soil (Index 1) See Section 3, p. 3-3. " ii. Uptake factor of pollutant in plant tissue (UP) Animal Diet: Radishes 0 ug/g tissue DW (ug/g soil DW)"1 Human Diet: Onion Tops and Bulbs 0 ug/g tissue DW (ug/g soil DW)"1 3-5 ------- In the only immediately available study of plant tissue uptake of MOCA (U.S. EPA, 1980), no MOCA residues could be found in onion tops and bulbs, radishes, or zucchini squash, all of which were grown in garden soil contaminated with MOCA. (See Section 4, p. 4-3.) d. Index 5 Values (ug/g DW) Sludge Application Rate (mt/ha) Sludge Diet Animal Human Concentration Typical Worst Typical Worst 0 0.0 0.0 0.0 0.0 5 0.0 0.0 0.0 0.0 50 0.0 0.0 0.0 0.0 500 0.0 0.0 0.0 0.0 e. Value Interpretation - Value equals the expected concentration in tissues of plants grown in sludge- amended soil. However, any value exceeding the value of Index 6 for the same or a similar plant species may be unrealistically high because it would be precluded by phytotoxicity. f. Preliminary Conclusion - The application of munici- pal sewage sludge to soil is not expected to result in increased concentrations of MOCA in plant tissue grown on the amended soil. 3. Index of Plant Concentration Permitted by Phytotoxicity (Index 6) a. Explanation - The index value is the maximum tissue concentration, in Ug/g DW, associated with phytotoxicity in the same or similar plant species used in Index 5. The purpose is to determine whether the plant tissue concentrations determined in Index 5 for high applications are realistic, or whether such concentrations would be precluded by phytotoxicity. The maximum concentration should be the highest at which some plant growth still occurs (and thus consumption of tissue by animals is possible) but above which consumption by animals is unlikely. b. Assumptions/Limitations - Assumes that tissue concentration will be a consistent indicator of phytotoxicity. 3-6 ------- c. Data Used and Rationale i. Maximum plant tissue concentration associated with phytotoxicity (PP) - Data not immediately available. d. Index 6 Values - Values were not calculated due to lack of data. e. Value Interpretation - Value equals the maximum plant tissue concentration which is permitted by phytotoxicity. Value is compared with values for the same or similar plant species 'given by Index 5. The lowest of the two indices indicates the maximal increase that can occur at any given application rate. f. Preliminary Conclusion - Conclusion was not drawn because index values could not be calculated. D. Effect on Herbivorous Animals 1. Index of Animal Toxicity Resulting from Plant Consumption (Index 7) a. Explanation - Compares pollutant concentrations expected in plant tissues grown in sludge-amended soil with feed concentration shown to be toxic to wild or domestic herbivorous animals. Does not con- sider direct contamination of forage by- adhering sludge. b. Assumptions/Limitations - Assumes pollutant form taken up by plants is equivalent in toxicity to form used to demonstrate toxic effects in animal. Uptake or toxicity in specific plants or animals may be estimated from other species. c. Data Used and Rationale i. Concentration of pollutant in plant grown in sludge-amended soil (Index 5) The pollutant concentration values used are those Index 5 values for an animal diet (see Section 3, p. 3-6). ii. Feed concentration toxic to herbivorous animal (TA) = 125 Ug/g DW Several studies have been conducted on the toxicity and/or carcinogenicity associated with the ingestion of MOCA. In a summary of this research (U.S. EPA, 1981), the lowest dietary 3-7 ------- concentration associated with neoplasia (i.e., long neoplasms or lung adenocarcinomas) in rats was a protein deficient diet containing 125 ppm of MOCA. Total incidence of neoplasms are sig- nificantly higher in rats on diets, either pro- tein adequate or deficient, with MOCA concentrations of 250 ppm. With the absence of more pertinent data, the dietary concentration of 125 ppm of MOCA in feed is used as a first approximation of the toxic feed concentration for herbivorous animals, although the validity of such generalization has yet to be established. (See Section 4, p. 4-5.) Index 7 Values Sludge Application Rate (mt/ha) Sludge Concentration 0 5 50 500 Typical Worst 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 e. Value Interpretation - Value equals factor by which expected plant tissue concentration exceeds that which is toxic to animals. Value > 1 indicates a toxic hazard may exist for herbivorous animals. f. Preliminary Conclusion - The consumption of plant tissue grown on sludge-amended, soils by herbivorous animals is not expected to pose a toxic hazard due to MOCA ingestion. Index of Animal Toxicity Resulting from Sludge Ingestion (Index 8) a. Explanation - Calculates the amount of pollutant in a grazing animal's diet resulting from sludge adhesion to forage or from incidental ingestion of siudge-amended soil and compares this with the dietary toxic threshold concentration for a grazing animal. b. Assumptions/Limitations - Assumes that sludge is applied over and adheres to growing forage, or that sludge constitutes 5 percent of dry matter in the grazing animal's diet, and that pollutant form in sludge is equally bioavailable and toxic as form used to demonstrate toxic effects. Where no sludge is applied (i.e., 0 mt/ha), assumes diet is 5 per- cent soil as a basis for comparison. 3-8 ------- Data Used and Rationale i. Sludge concentration of pollutant (SC) Typical 18.0 yg/g DW Worst 86.0 yg/g DW See Section 3, p. 3-1. ii. Fraction of animal diet assumed to be soil (GS) = 5% Studies of sludge adhesion to growing forage following applications of liquid or filter-cake sludge show that when 3 to 6 mt/ha of sludge solids is applied, clipped forage initially consists of up to 30 percent sludge on a dry- weight basis (Chaney and Lloyd, 1979; Boswell, 1975). However, this contamination diminishes gradually with time and growth, and generally is not detected in the following year's growth. For example, where pastures amended at 16 and 32 mt/ha were grazed throughout a growing sea- son (168 days), average sludge content of for- age was only 2.14 and 4.75 percent, respectively (Bertrand et al., 1981). It seems reasonable to assume that animals may receive long-term dietary exposure to 5 percent sludge if maintained on a forage to which sludge is regularly applied. This estimate of 5 percent sludge is used regardless of application rate, since the above studies did not show a clear relationship between application rate and ini- tial contamination, and since adhesion is not cumulative yearly because of die-back. Studies of grazing animals indicate that soil ingestion, ordinarily <10 percent of dry weight of diet, may reach as high as 20 percent for cattle' and 30 percent for sheep during winter months when forage is reduced (Thornton and Abrams, 1983). If the soil were sludge- amended, it is conceivable that up to 5 percent sludge may be ingested in this manner as well. Therefore, this value accounts for either of these scenarios, whether forage is harvested or grazed in the field. iii. Peed concentration toxic to herbivorous animal (TA) = 125 Ug/g DW See Section 3, p. 3-7. 3-9 ------- d. Index 8 Values Sludge Application Rate (rot/ha) Sludge Concentration 0 5 50 500 Typical Worst 0.0 0.0 0.0072 0.034 0.0072 0.034 0.0072 0.034 e. Value Interpretation - Value equals factor by which expected dietary concentration exceeds toxic concen- tration. Value > 1 indicates a toxic hazard may exist for grazing animals. 'f. Preliminary Conclusion - The consumption of crops to which sludge-amended soil or sludge adheres is not expected to pose a MOCA hazard to herbivorous animals. Effect on Humans 1. Index of Human Cancer Risk Resulting from Plant Consumption (Index 9) a. Explanation - Calculated dietary intake expected to result from consumption of crops grown on sludge- amended soil. Compares dietary intake with the cancer risk-specific intake (RSI) of the pollutant. b. Assumptions/Limitations - Assumes that all crops are grown on sludge-amended soil and that all those con- sidered to be affected take up the pollutant at the same rate. Divides possible variations in dietary intake into two categories: toddlers (18 months to 3 years) and individuals over 3 years old. c. Data Used and Rationale i. Concentration of pollutant in plant grown in sludge-amended soil (Index 5) The pollutant concentration values used are those Index 5 values for a human diet (see Section 3, p. 3-6). ii. Daily human dietary intake of affected plant tissue (DT) Toddler 74.5 g/day Adult 205 g/day 3-10 ------- The intake value for adults is based on daily intake of crop foods (excluding fruit) by vegetarians (Ryan et al., 1982); vegetarians were chosen to represent the worst case. The value for toddlers is based on the FDA Revised Total Diet (Pennington, 1983) and food groupings listed by the U.S. EPA (1984). Dry weights for individual food groups were estimated from composition data given by the U.S. Department of Agriculture (USDA) (1975). These values were composited to estimate dry- weight consumption of all non-fruit crops. iii. Average daily human dietary intake of pollutant (DI) - Data not immediately available. iv. Cancer potency = 0.325 (mg/kg/day) ~* A potency estimate of 0.325 (mg/kg/day)~^ was employed by the U.S. EPA Office of Toxic Sub- stances, as calculated from 70-year risk esti- mates presented in Table 1 of U.S. EPA, 1983b. (See Section 4, p. 4-3.) v. Cancer risk-specific intake (RSI) = 0.215 Ug/day The RSI is the pollutant intake value which results in an increase in cancer risk of 10"^ (1 per 1,000,000). The RSI is calculated from the cancer potency using the following formula: RSI = 1Q~6 x 70 kg x 103 ug/mg Cancer potency d. Index 9 Values - Values were not calculated due to lack of data. e. Value Interpretation - Value > 1 indicates a poten- tial increase in cancer risk of > 10~" (1 per 1,000,000). Comparison with the null index value at 0 mt/ha indicates the degree to which any hazard is due to sludge application, as opposed to pre- existing dietary sources. f. Preliminary Conclusion - Conclusion was not drawn because index values could not be calculated. 2. Index of Human Cancer Risk Resulting from Consumption of Animal Products Derived from Animals Feeding on Plants (Index 10) a. Explanation - Calculates human dietary intake expected to result from pollutant uptake by domestic 3-11 ------- animals given feed grown on sludge-amended soil (crop or pasture land) but not directly contaminated by adhering sludge. Compares expected intake with RSI. Assumptions/Limitations - Assumes that all animal products are from animals receiving all their feed from sludge-amended soil. Assumes that all animal products consumed take up the pollutant at the highest 'rate observed for muscle of any commonly consumed species or at the rate observed for beef liver or dairy products (whichever is higher). Divides possible variations in dietary intake into two categories: toddlers (18 months to 3 years) and individuals over 3 years old. Data Used and Rationale i. Concentration of pollutant in plant grown in sludge—amended soil (Index 5) The pollutant concentration values used are those Index 5 values for an animal diet (see Section 3, p. 3-6). ii. Uptake factor of pollutant in animal tissue (UA) - Data not immediately available. iii. Daily human dietary intake of affected animal tissue (DA) Toddler 43.7 g/day Adult 88.5 g/day The fat intake values presented, which comprise mea-t, fish, poultry, eggs and milk products, are derived from- the FDA Revised Total Diet (Pennington, 1983), food groupings listed by the U.S. EPA (1984) and food composition data given by USDA (1975). Adult intake of meats is based on males 25 to 30 years of age and that for milk products on males 14 to 16 years of age, the age-sex groups with the highest daily intake. Toddler intake of milk products is actually based on infants, since infant milk consumption is the highest among that age group (Pennington, 1983). iv. Average daily human dietary intake of pollutant (DI) - Data not immediately available. 3-12 ------- v. Cancer risk-specific intake (RSI) = 0.215 Ug/day See Section 3, p. 3-11. d. Index 10 Values - Values were not calculated due to lack of data. e. Value Interpretation - Same as for Index 9. f. Preliminary Conclusion - Conclusion was not drawn because index values could not be calculated. 3. Index of Human Cancer Risk Resulting from Consumption of Animal Products Derived from Animals Ingesting Soil (Index 11) a. Explanation - Calculates human dietary intake expected to result from consumption of animal products derived from grazing animals incidentally ingesting sludge-amended soil. Compares expected intake with RSI. b. Assumptions/Limitations - Assumes that all animal products are from animals grazing sludge-amended soil, and that all animal products consumed take up the pollutant at the highest rate observed for muscle of any commonly consumed species or at the rate observed for beef liver or dairy products (whichever is higher). Divides possible variations in dietary intake into two categories: toddlers (18 months to 3 years) and individuals over 3 years old. c. Data Used and Rationale i. Animal tissue - Data not immediately available. ii. Sludge concentration of pollutant (SC) A Typical 18.0 Ug/g DW Worst 86.0 Ug/g DW See Section 3, p. 3-1. iii. Background concentration of pollutant in soil = 2.9 yg/g DW See Section 3, p. 3-2. iv. Fraction of animal diet assumed to be soil (GS) = 5% See Section 3, p. 3-9. 3-13 ------- v. Uptake factor of pollutant in animal tissue (UA) - DaCa not immediately available. vi. Daily human dietary intake of affected animal tissue (DA) Toddler 39.A g/day Adult 82.4 g/day The affected tissue intake value is assumed to be from the fat component of meat only (beef, pork, lamb, veal) and milk products (Pennington, 1983). This is a slightly more limited choice than for Index 10. Adult intake of meats is based on males 25 to 30 years of age and the intake for milk products on males 14 to 16 years of age, the age-sex groups with the highest daily intake. Toddler intake of milk products is actually based on infants, since infant milk consumption is the highest among that age group (Pennington, 1983). vii. Average daily human dietary intake of pollutant (DI) - Data not immediately available. viii. Cancer risk-specific intake (RSI) = 0.215 ug/day See Section 3, p. 3-11. d. Index 11 Values- - Values were not calculated due to lack of data. e. Value Interpretation - Same as for Index 9. f. Preliminary Conclusion - Conclusion was n'ot drawn because index values could not be calculated. Index of Human Cancer Risk from Soil Ingestion (Index 12) a. Explanation - Calculates the amount of pollutant in the diet of a child who ingests soil (pica child) amended with sludge. Compares this amount with RSI. b. Assumptions/Limitations - Assumes that the pica child consumes an average of 5 g/day of sludge- amended soil. If the RSI specific for a child is not available, this index assumes the RSI for a 10 kg child is the same as that for a 70 kg adult. It is thus assumed that uncertainty factors used in deriving the RSI provide protection for the child, taking into account the smaller body size and any other differences in sensitivity. 3-14 ------- c. Data Used and Rationale i. Concentration of pollutant in sludge-amended soil (Index 1) See Section 3, p. 3-3. ii. Assumed amount of soil in human diet (DS) Pica child 5 g/day Adult 0.02 g/day The value of 5 g/day for a pica child is a worst-case estimate employed by U.S. EPA's Exposure Assessment Group (U.S. EPA, 1983a). The value of 0.02 g/day for an adult is an estimate from U.S. EPA, 1,984. iii. Average daily human dietary intake of pollutant (DI) - Data not immediately available. iv. Cancer risk-specific intake (RSI) = 0.215 ug/day See Section 3, p. 3-11. d. Index 12 Values - Values were not calculated due to lack, of data. e. Value Interpretation - Same as for Index 9. f. Preliminary Conclusion - Conclusion was not drawn because index values could not be calculated. 5. Index of Aggregate Human Cancer Risk (Index 13) a. Explanation - Calculates the aggregate amount of pollutant in the human diet resulting from pathways described in Indices 9 to 12. Compares this amount with RSI. * b. Assumptions/Limitations - As described for Indices 9 to 12. c. Data Used and Rationale - As described for Indices 9 to 12. d. Index 13 Values - Values were not calculated due to lack of data. e. Value Interpretation - Same as for Index 9. f. Preliminary Conclusion - Conclusion was not drawn because index values could not be calculated. 3-15 ------- II. LANDFILLING Based on the recommendations of the experts at the OWRS meetings (April-May,. 1984), an assessment of this reuse/disposal option is not being conducted at this time. The U.S. EPA reserves the right to conduct such an assessment for this option in the future. III. INCINERATION Based on the recommendations of the experts at the OWRS meetings (April-May, 1984), an assessment of this reuse/disposal option is not being conducted at this time. The U.S. EPA reserves the right to conduct such an assessment for this option in the future. IV. OCEAN DISPOSAL Based on" the recommendations of the experts at the OWRS meetings (April-May, 1984), an assessment of this reuse/disposal option is not being conducted at this time. The U.S. EPA reserves the right to conduct such an assessment for this option in the future. 3-16 ------- SECTION 4 PRELIMINARY DATA PROFILE FOR 4,4'-METHYLENE BIS(2-CHLOROANILINE) IN MUNICIPAL SEWAGE SLUDGE I. OCCURRENCE MOCA is a commercially important curing agent for Rappaport and polymer and epoxy-resin systems containing iso- Morales, 1978 cyanates. Production in 1972 estimated at 3.3 (p. 19) million kg. A. Sludge 1. Frequency of Detection Data not immediately available. 2. Concentration Sludge samples from Adrian, .MI U.S. EPA, 1980 (MOCA production plant nearby) in (p. 12) 1979 contained MOCA as follows: Return sludge - 0.006 Ug/g Digested sludge - 1.70 Ug/g Sludge (DW) - 18.00 Ug/g Sludge (DW) - 86.00 Ug/g Activated sludge, Adrian, MI, Parris et al., 18.0 Ug/g (DW) 1980 (p. 500) B. Soil - Unpolluted 1. Frequency of Detection Data not immediately available. However, it is known that herbicide- Hsu and Bartna, derived chloroaniline residues are 1974 (p. 444) immobilized by physical adsorption to both the organic and the inorganic fraction of the soil as well as by chemical binding to the soil organic matter and that this binding greatly increases their persistence in the environment. 2. Concentration In Adrian, MI, levels of MOCA in U.S. EPA, 1980 various soils in 1979 were as (p. 13) follows: 4-1 ------- Adrian roads, surface soil - <0.05-590 ug/g (WW) Garden soil from homes near MOCA plant - 0.08-2.90 ug/g (surface) 0.02-0.86 Ug/g (2-6 in. subsurface) 0.01-0.07 ug/g (6-10 in. subsurface) Adrian roads, surface - 13 ug/g (WW) (near MOCA plant) 2.1 Ug/g (WW) (1 mile from MOCA plant) Soil half-life = 5.3 years Water - Unpolluted 1. Frequency of Detection Data not immediately available. 2. Concentration a. Freshwater In Adrian, MI, levels of MOCA in various waters in 1979 were as follows: Industrial Site - deep well water surface runoff Sewage Treatment Plant (STP) - effluent water Raisin River Water (near STP outfall) b. Seawater Data not immediately available. c. Drinking water Data not immediately available. D. Air 1. Frequency of detection Data not immediately available. Versar, 1980 Parris et al., 1980 (p. 500) Ug/L 1.5 1.0 <0.5 4-2 ------- 2. Concentration In Adrian, MI, Levels of MOCA in the air near the MOCA plant in 1979' were A.57 Ug/m^ (method not cited) E. Food 1. Total Average Intake Data not immediately available. 2. Concentration In Adrian, MI, thoroughly washed samples of onion tops and bulbs, zucchini, and radishes from contami- nated gardens showed no evidence of MOCA residues. II. HUMAN EFFECTS A. Ingestion 1. Carcinogenicity Qualitative Assessment a. b. Sufficient evidence in three animal species; tumor induction at several sites. Potency A potency estimate of 0.325 (mg/kg/day)"^ was employed by the U.S. EPA Office of Toxic Substances as calculated from 70-year risk estimate presented in Table 1 of U.S. EPA, 1983b. Effects Malignant lung adenocarcinomas, primary lung neoplasms, mammary adenocarcinomas, hepatocellular carcinomas and Zymbal gland car- cinomas were found in rats. 2. Chronic Toxicity Data not presented since carcinogenic potency will be used to assess hazard. U.S. EPA, 1980 (p. 14) U.S. EPA, 1980 (p. 36) U.S. EPA, 1983b (p. 15) U.S.EPA, 1983b (p. 17) U.S. EPA, 1983b (p. 20) 4-3 ------- B. 3. Absorption FactOT Data not immediately available. 4. Existing Regulations "MOCA is an animal carcinogen and has been banned in food and food-contact surfaces by the FDA." Inhalation 1. Carcinogenicity Qualitative assessment a. c. Not tested for carcinogenicity by inhalation route. Some indica- tion of bladder cancer from occu- pational exposure in humans. Potency Not derived for inhalation route. However, the U.S. EPA Office of Toxic Substances has employed the oral potency value to estimate risk, of human inhalation exposure, assuming 100 percent absorption of inhaled MOCA. Effects Not tested in animals by the inhalation route. Possible bladder cancer in humans. 2. Chronic Toxicity Data not immediately available. 3. Absorption Factor Assumed to be 100 percent. 4. Existing Regulations Manufacture temporarily banned by State of Michigan in 1979. Parris et al., 1980 (p. 497) U.S. EPA, 1983b (p. 11, 14) U.S. EPA, 1983b (p. 17) U.S. EPA, 1983b (p. 11, 14) U.S. EPA, 1983b (p. 17) U.S. EPA, 1983b (p. 3) 4-4 ------- III. PLANT EFFECTS A. Phytotoxicity Data not immediately available. B. Uptake In Adrian, MI, thoroughly washed samples of U.S. EPA, 1980 onion tops and bulbs, zucchini, and radishes (p. 36) from contaminated gardens showed no evidence of MOCA residues. IV. DOMESTIC ANIMAL AND WILDLIFE EFFECTS A. Toxicity LD50: 750 Ug/kg (oral) - rats U.S. EPA, 1981 5000 Ug/kg (dermal) - rabbits (p. 8) Lowest-observed-adverse-effect levels U.S. EPA, 1981 (LOAEL) for tumors (pp. 9-11) Mice: 200 ppm (diet) Rats: 500 ppm (diet) Dogs: 8 to 15 pg/kg/day (oral) Rats: 25.0 ppm (protein adequate diet) 125 ppm (protein inadequate diet) B. Uptake Data not immediately available. V. AQUATIC LIFE EFFECTS Data not immediately available. VI. SOIL BIOTA EFFECTS Data not immediately available. VII. PHYSICOCHEMICAL DATA FOR ESTIMATING FATE AND TRANSPORT Molecular wt: 267 Rappaport and Density: 1.44 g/mL at 24°C Morales, 1978 Melting point: 100 to 109°C (p. 19-20) Vapor pressure: 3.7 x 10~6 mm Hg at 20"C 5.1 x 10~6 mm Hg at 30°C Soil half-life: 5.3 years Versar, 1980 4-5 ------- SECTION 5 REFERENCES Bertrand, J. E., M. C. Lutrick, G. T. Edds and R. L. West. 1981. Metal Residues in Tissues, Animal Performance and Carcass Quality with Beef Steers Grazing Pensacola Bahigrass Pastures Treated with Liquid Digested Sludge. J. Ani. Sci. 53:1. Boswell, F. C. 1975. Municipal Sewage Sludge and Selected Element Applications to Soil: Effect on Soil and Fescue. J. Environ. Qual. 4(2):267-273. Chaney, R. L., and C. A. Lloyd. 1979. Adherence of Spray-Applied Liquid Digested Sewage Sludge to Tall Fescue. J. Environ. Qual. 8(3):407- 411. Hsu, T., and R. Bartha. 1974. Interaction of Pesticide-Derived Chloroaniline Residues with Soil Organic Matter. Soil Science 116(6):444-452. Parris, G. E., G. W. Diachenko, R. C. Entz et al. 1980. Waterborne Methylene Bis(2-Chloroaniline) and 2-Chloroaniline Contamination Around Adrian, Michigan. Bull. Environ. Contam. Toxicol. 24:497-503. Pennington, J.A.T. 1983. Revision of the Total Diet Study Food Lists and Diets. J. Am. Diet. Assoc. 82:166-173. Rappaport, S. M., and R. Morales. 1978. Air-Sampling and Analytical Method for 4,4-Methylene Bis(2-Chloroaniline). Analytical Chem. 51(1): 19-23. Ryan, J. A., H. R. Pahren, and J. B. Lucas. 1982. Controlling Cadmium in the Human Food Chain: A Review and Rationale Based on Health Effects. Environ. Res. 28:251-302. Thornton, E., and P. Abrams. 1983. Soil Ingestion - A Major Pathway of Heavy Metals into Livestock Grazing Contaminated Land. Sci. Total Environ. 28:287-294. U.S. Department of Agriculture. 1975. Composition of Foods. Agricultural Handbook No. 8. U.S. Environmental Protection Agency. 1980. Potential Health Effects from Persistent Organics in Wastewater and Sludges Used for Land Application. EPA 600/1-80-025. U.S Environmental Protection Agency, Cincinnati, OH. U.S. Environmental Protection Agency. 1981. Chemical Hazard Informa- tion Profile: 4,4* Methylene Bis(2-Chloroaniline). Draft Report. Environmental Criteria and Assessment Office. U.S. Environmental Protection Agency, Cincinnati, OH. February 8. 5-1 ------- APPENDIX PRELIMINARY HAZARD INDEX CALCULATIONS FOR 4,4'-METHYLENE BIS (2-CHLOROANILINE) IN MUNICIPAL SEWAGE SLUDGE I. LANDSPREADING AND DISTRIBUTION-AND-MARKETING A. Effect on Soil Concentration of 4,4'-Methylene Bis (2-Chloroani 1 ine ) 1. Index of Soil Concentration (Index 1) a. Formula (SC x AR) + (BS x MS) - G!SS ~ AR -f MS CSr = CSS [1 + 0.5 where: CSS = Soil concentration of pollutant after a single year's application of sludge (Ug/g DW) CSr = Soil concentration of pollutant after the yearly application of sludge has been repeated for n + 1 years (ug/g DW) SC = Sludge concentration of pollutant (ug/g DW) AR = Sludge application rate (mt/ha) MS = 2000 mt ha/DW = assumed mass of soil in upper 15 cm BS = Background concentration of pollutant in soil (ug/g DW) t^. = Soil half-life of pollutant (years) n = 99 years b. Sample calculation CSS is calculated for AR = 0, 5, and 50 mt/ha only •» ai7ft«flA ., / TMJ - (18 Ug/g DW x 5 mt/ha) + (2.9 ug/g DW x 2000 mt/ha) 2. 93765586 Ug/g DW - (J mj./ha QW + 200Q mt/ha ^ CSr is calculated for AR = 5 mt/ha applied for 100 years 23.9629350 ug/g DW = 2.93765586 ug/g DW [1 + 0.5(1/5'3) + 0.5(2/5'3) + ... + 0.5(99/5-3)] A-l ------- B. Effect on Soil Biota and Predators of Soil Biota 1. Index of Soil Biota Toxicity (Index 2) a. Formula 1^ Index 2 = — where: I± = Index 1 = Concentration of pollutant in sludge-amended soil (pg/g DW) TB = Soil concentration toxic to soil biota (yg/g DW) b. Sample calculation - Values .were not calculated due to lack of data. 2. Index of Soil Biota Predator Toxicity (Index 3) a. Formula T , , *1 x UB Index 3 = —~ where: II = Index 1 = Concentration of pollutant in sludge-amended soil (ug/g DW) UB = Uptake factor of pollutant in soil biota (yg/g tissue DW [ug/g soil DW]"1) TR = Feed concentration toxic to predator (ug/g DW) b. Sample calculation - Values were not calculated due to lack, of data. C. Effect on Plants and Plant Tissue Concentration 1. Index of Phytotoxic Soil Concentration (Index 4) a. Formula Index 4 = — where: II = Index 1 = Concentration of pollutant in sludge-amended soil (ug/g DW) TP = Soil concentration toxic to plants (yg/g DW) A-2 ------- b. Sample calculation - Values were not calculated due to lack of data. 2. Index of Plant Concentration Caused by Uptake (Index 5) a. Formula Index 5 = Ii x UP where: 1^ = Index 1 = Concentration of pollutant in sludge- amended soil (ug/g DW) UP = Uptake factor of pollutant in plant tissue (Ug/g tissue DW [ug/g soil DW]"1) b. Sample Calculation 0 Ug/g DW = 2.9 Ug/g DW x 0 ug/g tissue DW (ug/g soil DW)'1 3. Index of Plant Concentration Increment Permitted by Phytotoxicity (Index 6) a. Formula Index 6 = PP where: PP = Maximum plant tissue concentration associ- ated with phytotoxicity (ug/g DW) b. Sample calculation - Values were not calculated due to lack of data. D. Effect on Herbivorous Animals 1. -Index of Animal Toxicity Resulting from Plant Consumption (Index 7) a. Formula Index 7 = where: 15 = Index 5 = Concentration of pollutant in plant grown in sludge-amended soil (ug/g DW) TA = Feed concentration toxic to herbivorous animal (ug/g DW) A-3 ------- b. Sample calculation n - 0 Ug/g DW " 125 Ug/g DW 2. Index of Animal Toxicity Resulting from Sludge Ingestion (Index 8) a. Formula If AR = 0; Index 8=0 SC x GS If AR £ 0; Index 8 = TA where: AR = Sludge application rate (mt DW/ha) : SC = Sludge concentration of pollutant (yg/g DW) GS = Fraction of animal diet assumed to be soil TA = Feed concentration toxic to herbivorous animal (ug/g DW) b. Sample calculation If AR = 0; Index 8=0 I£ a , „ 0.0072 . iB E. Effect on Humans 1. Index of Human Cancer Risk Resulting from Plant Consumption (Index 9) a. Formula (I5 x DT) + DI Index 9 = - — - where: 15 = Index 5 = Concentration of pollutant in plant grown in sludge-amended soil (ug/g DW) DT = Daily human dietary intake of affected plant tissue (g/day DW) DI = Average daily human dietary intake of pollutant (ug/day) RSI = Cancer risk-specific intake (ug/day) b. Sample calculation (toddler) - Values, were not calculated due to lack of data. A-4 ------- 2. Index of Human Cancer Risk Resulting from Consumption of Animal Products Derived from Animals Feeding on Plants (Index 10) a. Formula (15 x UA x DA) + DI Index 10 = _ where: 15 = Index 5 = Concentration of pollutant in plant grown in sludge-amended soil (ug/g DW) UA = Uptake factor of pollutant in animal tissue (Ug/g tissue DW [ug/g feed DW]"1) DA = Daily human dietary intake of affected animal tissue (g/day DW) (milk products and meat, poultry, eggs, fish) DI = Average daily human dietary intake of pollutant (ug/day) RSI = Cancer risk-specific intake (ug/day) b. Sample calculation (toddler). - Values were not calculated due to lack of data. 3. Index of Human Cancer Risk Resulting from Consumption of Animal Products Derived from Animals Ingesting Soil (Index 11) " a. Formula _. AD . _ , .. (BS x GS x UA x DA) + DI If AR = 0; Index 11 = — KbJL _, AD , n , , ., (SC x GS x UA x DA) + DI If AR f 0; Index 11 = where: AR = Sludge application rate (mt DW/ha) BS = Background concentration of pollutant in soil (yg/g DW) SC = Sludge concentration of pollutant (ug/g DW) GS = Fraction of animal diet assumed to be soil UA = Uptake factor of pollutant in animal tissue (Ug/g tissue DW [ug/g feed DW]"1) DA = Daily human dietary intake of affected animal tissue (g/day DW) (milk products and meat only) DI = Average daily human dietary intake of pollutant (jag/day) "RSI = Cancer risk-specific intake (ug/day) b. Sample calculation (toddler) - Values were not calculated due to lack of data. A-5 ------- 4. Index of Human Cancer Risk. Resulting from Soil Ingestion (Index 12) a. Formula (Ii x DS) + DI RSI where: 1^ = Index 1 = Concentration of pollutant in sludge-amended soil (ug/g DW) DS = Assumed amount of soil in human diet (g/day) DI = Average daily human dietary intake of pollutant (yg/day) RSI = Cancer risk-specific intake (yg/day) b. Sample calculation (toddler) - Values were not calculated due to lack of data. 5. Index of Aggregate Human Cancer Risk (Index 13) a. Formula 3DI Index 13 = Ig + I10 + In + Ij.2 ~ ( RSI where: Ig = Index 9 = Index of human toxicity/cancer risk resulting from plant consumption (unitless) = Index 10 = Index of human toxicity/cancer risk resulting from consumption of animal products derived from animals feeding on plants (unitless) = Index 11 = Index of human toxicity/cancer risk resulting from consumption of animal products derived from animals ingesting soil (unitless) = Index 12 = Index of human toxicity/cancer risk resulting from soil ingestion (unitless) DI = Average daily human dietary intake of pollutant (yg/day) RSI = Cancer risk-specific intake ~(yg/day) b. Sample calculation (toddler) - Values were not calculated due to lack of data. A-6 ------- II. LANDPILLING Based on the recommendations of the experts at the OWRS meetings (April-May, 1984), an assessment of this reuse/disposal option is not being conducted at this time. The U.S. EPA reserves the right to conduct such an assessment for this option in the future. III. INCINERATION Based on the recommendations of the experts at the OWRS meetings (April-May, 1984), an assessment of this reuse/disposal option is not being conducted at this time. The U.S. EPA reserves the right to conduct such an assessment for this option in the future. IV. OCEAN DISPOSAL Based on the recommendations of the experts at the OWRS meetings (April-May, 1984), an assessment of this reuse/disposal option is not being conducted at this time. The U.S. EPA reserves the right to conduct such an assessment for this option in the future. A-7 ------- |