ENVIRONMENTAL PROTECTION AGENCY OFFICE OF ENFORCEMENT EPA-330/1-77-009 Reconnaissance Environmental Levels Of Nitrosamines In The Southeastern United States NATIONAL ENFORCEMENT INVESTIGATIONS CENTER DENVER, :o:0RAD0 __ ------- Environmental Protection Agency Office of Enforcement EPA—330/1—?7—009 RECONNAISSANCE OF ENVIRONMENTAL LEVELS OF NITROSAMINES IN THE SOUTHEASTERN UNITED STATES August 1977 National Enforcement Investigations Center Denver, Colorado ------- CONTENTS I. INTRODUCTION II. BACKGROUND 1 2 III. FIELD STUDIES Ciba-Geigy Corp Martin-Marietta (SODYECO) Proctor Chemical Co., Inc. Velsicol Chemical Co. Farmers Supply and Produce 4 4 13 18 30 32 IV. SUMMARY AND CONCLUSIONS . REFERENCES TABLES 35 37 1 Monitoring Site Description - Ciba Geigy Corp. . . . 2 Monitoring Site Description - Martin-Marietta Corp. 3 Monitoring Site Description - Lumber Street Plant . 4 Monitoring Site Description - Cedar Springs Plant . 5 Monitoring Site Description - Velsicol Chemical Co. FIGURES . . . . . . . . 10 19 28 29 33 1 Wastewater Treatment Schematic - Ciba-Geigy Corp. 2 General Plant Layout - Ciba-Geigy Corp. 3 Wastewater Treatment Schematic — Martin-Marietta Corp. SODVECO Division 4 General Plant Layout - Martin-Marietta Corp. SODVECO Division 5 General Plant Layout — Proctor Chemical Co. Lumber St. Plant 6 General Plant Layout - Proctor Chemical Co. Cedar Springs Plant 7 Typical Amine Reaction Sequences — Proctor Chemical Co., Inc. Salisbury, N.C. 7 11 15 20 22 23 26 ------- I. INTRODUCTION In 1976, the Environmental Protection Agency (EPA), National Enforce- ment Investigations Center (NEIC) conducted investigations to determine environmental levels of nitrosanhines in the Central United States.’ The data from the investigations showed that there was little indication of N—nitroso compounds in the air in the vicinity of the numerous sources ex- amined, even on those occasions when these compounds were observed in plant effluent. The water samples indicated that there were primary sources of direct emissions to the environment of a number of N-nitroso compounds. It was concluded that these compounds probably arose as im- purities during the synthesis of other compounds and they were emitted to the environment during the use or modification of these products. These N—nitroso compounds were observed in chemical, pesticide and coke plant effluents, some consistently. The EPA Region IV Administrator identified potential dischargers of nitrosanilnes in the southeastern United States, and because of the above experience, requested that NEIC conduct air and water monitoring investi- gations to determine if the compounds were being released to the en- vi ronment. The five industrial facilities monitored in April and May 1977 by NEIC were: 1. Ciba-Geigy Corporation, McIntosh, Alabama 2. Martin—Marietta (SODYECO), Charlotte, North Carolina 3. Proctor Chemical Company, Salisbury, North Carolina 4. Velsicol Chemical Company, Chattanooga, Tennessee 5. Farmers Supply and Produce, Monticello, Kentucky ------- II. BACKGROUND Nitrosamines are a class of organic compounds containing the N - N = 0 linkage and having the general structure R - R’’ - N — 0 Since Rand R’ can represent alkyl, aryl or cyclic groups, the nitro- samine compounds have widely varying chemical, physical and toxicologi- cal properties. Nitrosamines are relatively stable, resisting reduction, moderate temperature oxidation (less than 300°C) and pyrolysis at even higher temperatures. They are very photoreactive in water or in the atmosphere. Nitrosamines are formed naturally in moist air and in soil and water in which secondary and/or tertiary amines and nitrites exist or are being formed. Only two N-nitroso compounds have been produced in significant quantities for industrial or manufacturing purposes. Diphenylnitrosamine (DPN or N-nitrosodiphenylamine) is produced by the rubber industry but has not proved carcinogenic to test animals. Di- methylnitrosamine (DMN or N-nitrosodimethylamine) has been identified as an air pollutant in Baltimore, Maryland and Belle, West Virginia. Because 0MM has been shown to be carcinogenic to laboratory animals, its presence as an air pollutant is cause for concern. Following the studies of the only known primary source of the carcinogenic nitrosamine (the FMC Corporation in Baltimore, Maryland), investigations have turned to precursor sources, i.e. mainly sources of secondary amines. Sources of primary and tertiary amines are of ------- 3 less interest if nitrosation is considered to occur via reaction with nitrous acid in the environment. Unlike secondary amines which can form nitrosamines, the primary aliphatic and aromatic aniines yield other products and only a few tertiary anlines form nitrosamines. If other reaction mechanisms are hypothesized to yield nitrosamines, e.g., with metallic compounds, the number of possible precursors would be expanded. However, there is no indication of measurable levels of these nitroso compounds in environmental samples to date. The health effects of the ambient levels reported to date are still unknown. Of more than 100 of these N-nitroso compounds synthesized, over 70% have been shown to be carcinogenic to some animal species. In laboratory tests, this class of compounds has produced cancer in all - animal species tested. ------- III. FIELD STUDIES * Samples were collected from four of the five industrial facili- ties to determine nitrosamine levels in both the ambient air and the water. Air samples were collected over a 2-hr period using foil— ** covered impingers filled with 60 ml of iN KOH. The air samples were drawn through the impingers by a vacuum pump and the flows con- trolled by a calibrated stainless steel hypodermic needle. Water and wastewater samples were collected on a grab basis in amber glass quart *** bottles with Teflon liners. The NEIC analytical procedure for ni- trosamines is included in Appendix A. Because the monitoring for nitrosamines was conducted on a “screening” type basis to determine if the compounds were present, detailed process evaluations were not made. In addition, due to the proprietary nature of the processes, Company ‘personnel were reluctant. to discuss processes or the types and amounts of materials used. In several plants, N-nitroso compounds were found in wastewater samples; in-plant sampling would be required to locate th& sources of these compounds. With the exception of one sample at Ciba—Geigy Corporation, N-nitroso compounds were not detected in the air samples. CIBA-GEIGY CORPORATION The Ciba-Geigy Corporation is an international organization which * Samples were not collected from Farmers Supply and Produce. ** Impingers covered with foil to prevent photoreaction. Teflon is a trade name. ------- 5 originates, manufactures and markets organic chemical specialties. The McIntosh plant began operating in 1952 and produced only DDT. In the early 60’s, DDT production ceased after newer and more effective in- secticides were developed. The McIntosh plant, one of the larger Ciba-Geigy facilities, pro- duces more than 75 different products including agricultural chemicals, dyestuffs, plastics and additives, and sequestrene products. Herbicides include Triazine and Fluometuron; the basic insecticides manufactured * * are Diazinon, Spectracide, and Chlorobenzilate. Fluorescent whitening agents are manufactured for detergents, and other optical brighteners are produced for use in the textile and paper industries. The plant operates 24 hr/day, 7 days/week. Water Supply and Wastewater Treatment Water used for cooling purposes is pumped to a large reservoir from the Tombigbee River, and then pumped to the plant and used on a once- through basis. The spent cooling water is returned to the river via National Pollutant Discharge Elimination System (NPDES) Outfall 001; the flow is variable, but averages 7.6 x 1O 4 m 3 /day (20 mgd). Approximately 2.3 x l0 m 3 /day (6 mgd) of water is withdrawn from the reservoir, clarified, filtered, and demineralized, and used for boiler make-up. An additional 2.3 x 1O 4 m 3 /day is pumped from five wells. The pH is adjusted with soda ash, the water is degassified and chlorinated, and then is used in the processes and also as the potable supply. * Trade name. ------- 6 All process wastewater is collected in segregated sewers and dis- charged to one of three treatment systems [ Figure 1]. Some process wastewaters are collected in a common sewer and flow to an equaliza- tion pond. An auxiliary pond, located upstream of the equalization pond, receives process wastewaters high in ammonia; this wastewater is released into the equalization pond under controlled conditions be- cause the treatment system does not reduce the ammonia. This method is used to bring the effluent into compliance with the NPDES limita- tions for ammonia. After equalization, the wastewater is neutralized, aerated for 10 days, and then polished an additional 5 days in another aerated lagoon. Finally, the wastewater is clarified, neutralized, and dis- charged through Outfall 001. Wastewater from the Diazinon process and wastewaters containing cyanide are discharged to the detoxification system. The acidic wastewaters flow to the destruct basin for mixing purposes. After 20 * days, the flow is sent to the alkaline chlorination system for CN destruction. After detoxification, the wastewater is sent to the equalization pond. Dilute process wastewaters, designated by the Company as slightly contaminated, along with stormwater runoff and water from the cascade coolers, flow to a large holding pond. Since the dilute wastewater is slightly acidic, spills are routed to the holding pond and mixed with dilute wastewater. The spilled materials are less stable in an acid environment. * This system installed for plant upsets and is not required under normal operating conditions. Acidic wastewaters are not mixed with wastewaters containing cyanide. ------- 7 WA TC TWM wig.AK A IO A L LU FIGURE 1 3A ve3 S64.l FRbM sUE.Q W*TLL r&eATMeN V CIBA-GEIGY CORPORATION McINTOSH, ALABAMA WASTE WATER TREATMENT SCHEMATIC 0.2 .5 Acre C RD U J D 0 r — — — — — — — 41 1 _____.* — — E GUP Soi..to TO C TA W8*. ------- 8 All wastewaters combine with the spent, once—through cooling water, and flow to the river, about 1.2 km (0.75 mi) from the treatment area. Sanitary wastewaters are treated in 9 extended aeration package plants which discharge to the equalization pond. The package plants are designed to treat a total of 187 m 3 /day (49,500 gpd). Solid Waste Disposal The Company’s policy is that solid wastes are not to be removed from the property for disposal or treatment. All flammable material, toxic and nontoxic, is burned in a multipurpose, gas—fired incinerator equipped with primary and secondary burners. Emission control equip- ment consists of a water quench tank followed by a high-energy venturi water scrubber and a packed tower using a caustic scrubbing solution. Nonburnables are buried in a landfill located on the northeast section of the property. The site has been classified by the State as accept- able for hazardous and toxic wastes. Processes There are more than 25 processes, all batch operated. Products from this facility include Diazinon, herbicides, thioherbicides, atrazine, sequesterines and whitening agents. Raw or intermediate materials containing amines used in their processes include: Monoethyl amine Isopropylamine Secondary butylamine n-methyl ethanol amine Cyc 1 opropyl methyl —n-propyl amine Propyl amine Ethylene diamine Anal me ------- 9 Morphal me Di methyl amine Tn ethanol amine Di ethanolami ne Meta amino benzo trifluoride Diaminostilbene disulfonic acid Diethylenetriami ne Ami noethyl ethanol amine Pyrrol idine Other amines considered proprietary These compounds are all active ingredients, but are not used all the days the plant is operating. However, during the NEIC monitoring period, processes using amines were operating. According to plant personnel, the only nitrating agent used by the facility is sodium nitrite for one of their brightener reactions. This agent is used periodically. Insignificant quantities of nitric acid are used through- out the plant; ammonia is used on—site for refrigeration and other processes. Monitoring Results Monitoring was conducted on May 25, 1977; a description of the air and water monitoring sites is given in Table 1 and shown in Figure 2. The air speed varied between 4.8 and 16 km (3 and 10 mi)/hr, and the wind was mainly from the southwest. The temperature during the monitor- ing period was between 85° and 90°F; the sky was cloudy. Nitrosamines were not detected in the untreated or treated well and river water samples nor in the ambient air samples collected at the east, north, and west monitoring sites. In the grab sample collected * from the treated wastewater effluent, 0.05 ugh dimethylnitrosamine ** (DMN) and 0.63 pg/i nitrosopyrrolidine (NPyr) were detected. A mass * Detection limit - 0.05 pg/i. ** Detection limit — 0.1 jig/i. ------- 10 Table 1 MONITORING SITE DESCRIPTION CIBA-GEIGY CORPOR4TION Mclntoeh, Alabc na Sample Description Site Location Untreated well water Well water surn , next to degassifier, Drior to degassification Treated well water Primary pump station Untreated river water Punp house at reservoir Treated river water Clear well, east of filtration niant Treated wastewater effluent Effluent ditch, about 1/4 mile from river, at bridge Air - south of processes Ditch on south side of plant at fence line (around level) Air - east of processes Roof of filtration building Air - north of processes North side of chanqe room #8 (ground level) Air - west of processes North side of Brown and Root iuard shack (qround level ------- c nn ouor,’8 0’ K K K K I I L..J Ii ’ K K I K M K FRo ES9Es l a s — — - — — — — — — — — — — —. — — FIGURE 2 -‘ CIbA-GEIGY CORPORATION GENERAL PLANT LAYOUT McINTOIH, ALAbAMA TO WP TfW4 Til Tt .ArM&,.r $Y TEM LI PLANT • AIR MONITORING SITE -J ------- 12 * of 0.02 pg DMN was detected in the air sample collected at the south monitoring site. However, these levels were too low to be confirmed by mass spectrometry. An unidentifiable nitrosamine was also detected in the wastewater effluent, but in a lesser concentration than NPyr. Since the intake waters did not contain nitrosamines, the source of the N-nitroso compounds in the effluent must have originated in the processes. The process wastewater comprises about 12% of the total effluent flow of 93,000 m 3 /day (24.5 mgd). If the N-nitroso compound concentrations are assumed to be constant in the effluent, then the concentrations of DMN and NPyr in the process wastewater would be as high as 0.42 and 5.3 pg/l, respectively. The wind direction during monitoring was variable, but mainly from the southwest. The DMN was detected in the air sample upwind of the processes. Olin Chemical is located about 0.8 km (0.5 ml) south of the Ciba-Geigy facility; however, whether the nitrosamine originated from Olin, or Ciba-Geigy, is not known. Approximately 472 liters of air was drawn through the impingers [ Appendix B - sample volumes], therefore, the concentration of DMN was 42 ng/m 3 which is in the range of 40 to 300 ng/m 3 found at Baltimore, Maryland and Belle, West Virginia. 2 ’ 3 Based on the one positive sample, it cannot be concluded that nitrosamines are present at low levels or are ubiquitous in the plant’s environment. It is equally incorrect to infer that nitrosamines are not present based on the three negative samples. The negative results at the other three sites indicate that: 1) nitrosamines are not emitted, 2) nitrosamines were not emitted during sampling, 3) once in the atmosphere these com- pounds decomposed rapidly, or 4) the compounds were present, but not collected by the impingers due to environmental conditions. How- ever, DMN is a known carcinogen to laboratory animals, therefore its * Detection limit (in air sample) - 0.02 pg. ------- 13 presence indicates some degree of risk and Ciba-Geigy should take action to eliminate the emission of nitrosamines. Since only a screening type of monitoring was conducted, the maximum levels or sources, of N-nitroso compounds emitted, cannot be determined. Ciba—Geigy personnel collected air samples concurrently with NEIC; therefore, they have the monitoring and analytical capability to determine sources and atmospheric levels of nitrosamines. MARTIN-MARIETTA (SODYECO ) The SODYECO Division of Martin-Marietta Corporation began manufac- turing liquid sulfur dyes for the textile industry in 1936; the Company was known as Southern Dyestuff Company. SODYECO now produces over 200 organic chemical compounds and textile dyes. There are between 30 and 40 organic chemicals produced, including pesticides. The pesticides are prepared under contract to other companies while the dyestuffs are prepared for general sales. The plant is located on 182 ha (450 acres) on the east side of the Catawba River and south of highway 27 in Mt. Holly (NW of Charlotte). Approximately 12 to 14 ha (30 to 35 acres) of the site is dedicated to manufacturing processes and supportive facilities. An additional 12 to 14 ha consists of lagoons for process wastewater treatment. The plant operates 3 shifts, 7 days/week. There are approximately 190 processes used at the plant, all of which are batch operated. The average production capacity is rated at 333,000 kg (734,000 lb)/day of finished product. Water Supply and Wastewater Treatment All water used in the plant for domestic purposes is obtained from ------- 14 wells; the water is not treated. Process water and cooling water is withdrawn from the Catawba River, coagulated and filtered. Sanitary wastes are discharged to various septic tanks throughout the plant; septic tank effluent is discharged to the process alkaline wastewater sewers. All process wastewaters are treated prior to discharge to the Catawba River. The single outfall is authorized by a Federal NPDES per- mit; currently the effluent complies with all of the limitations except BOD. BOD limitations are generally met during the warmer months. There are three process wastewater streams: the thiosulfate waste stream, the weak acid stream, and the alkaline waste stream [ Figure 3]. The thiosulfate waste stream is collected in a holding pond and then sent to a aerated lagoon where the wastewater is biologically converted to 1% I-1 2 S0 4 and sodium thiosulfate at pH 1 to 2. The weak acid stream is collected in two lagoons; the biologically converted effluent is combined with the effluent from weak acid lagoons and neutralized with ground limestone in a concrete basin. The neutralized effluent is sent to a 6.9 ha (17 acre) lagoon and the gypsum settled. The supernatant from the 6.9 ha lagoon is combined with the alkaline waste stream and sent to a flow equalization and aeration basin. The flow is then routed to an extended aeration-activated sludge lagoon; sludge is settled in a steel Permutit Company clarifier. Post settling and post aeration lagoons follow the clarification process. After final settling, the effluent is discharged to the Catawba River, about 0.54 km (0.33 mi) downstream from the final settling lagoon. The flow averages 7,570 rn 3 /day (2 rngd). The EPA has provided a grant to the Company to help fund this treatment system. All herbicide wastewaters are incinerated. The incinerator is operated only when the holding tank for the wastewaters becomes full. ------- 15 FIGURE 3 MARTIN MARIETTA CORPORATION SODYECO DIVISION CHARLOTTE, N. CAROLINA WASTE WATER TREATMENT SCHEMATIC 5LUP4e FROM •1 OX I C. wkrea. ‘.0 £%VE PIU)Tt EFcL. ------- 16 The incinerator is fired with No. 2 fuel oil; it is equipped with once- through, dilute caustic spray scrubber with two packed sections. The spent caustic is sent to the wastewater treatment system. Processes Of the more than 190 processes, secondary amines are used in only 5 major process reactions; the end products are either sent out of the plant as finished product or used in other plant processes. There are also at least 25 other processes which use tertiary amines in the re- actions. Company personnel stated that all of the reactions are pro- prietary, therefore only a general description was provided with the emphasis on the possibilities of amines being emitted to the air or discharged in the wastewater. There is a possibility of nitration of secondary amines released to the environment because one of SODYECY’s specialties is nitration. According to Company personnel, the adjacent industries do not use nitric acid, nitrogen compounds, or secondary amines. The 5 reactions using secondary amines are discussed briefly: 1. Di—n-propylamine. This amine is very volatile and the reaction is conducted in a closed system. Safety valves and pop valves are vented directly to the atmosphere. The amine attaches to the benzene ring and becomes part of the product, Oryzalin, a powdered herbicide. During the process, the product is filtered. The liquid filtrate is sent to the incinerator. Other wastewaters generated in the process before the herbicide becomes active are sent to the treatment ponds. The flow, about 115 m 3 /day 30,000 gpd), could contain amines. ------- 17 The process(s) using this amine was operating during the monitoring period. 2. n-cyanoethylorthochloroanaline. This amine is used as a coupler in the production of a dispersed dye. Between 5 and 10% of the final product consists of this amine. Since the emission sources from the reaction train are not equipped with control devices, the possibility exists that the amine may be emitted. During the reaction, wastewater is discharged to the treatment system; the majority of the flow originates from the plate and frame filter press. The total flow is unknown, but is highly variable. The process was operating up to the day of NEIC’s monitoring, but was down on the monitoring day. 3. Diphenylamine. The amine is used in the production of sulfur dyes. The off-gases from the reaction are vented to the atmosphere. Filtrate, approximately 11 m 3 /day (3,000 gpd) from the plate and frame filters, is sent to the treatment system. Since the process reaction occurs at 0°C and the amine has a low vapor pressure, emissions to the air are not probable. The process was operating during NEIC’s monitoring. 4. Parahydroxyphenylamine. The amine is added in a rotary thionator (closed system) in the production of dyes. The reaction occurs in a high temperature ball mill; the off-gases are vented to caustic absorbers. The spent absorbent is used in other process reactions and not discharged. Thereare no wastewater streams from this process. This process was operating during NEIC’s inspection. ------- 18 5. Carbazole. This low vapor pressure amine is used as a raw material in several reactions, including the production of sulfur dyes and organic chemicals. Company personnel stated that this amine could possibly be emitted and also discharged in the wastewater stream. The material was being used during NEIC’s monitoring. Monitoring Results Monitoring was conducted on May 5, 1977; a description of the air and water monitoring sites is given in Table 2 and shown in Figure 4. The air speed varied between 8 and 24 km (5 and 15 nii)/hr and the wind was mainly from the southwest. The temperature was 75°F. Sky con- ditions were clear; however, it had rained 0.11 inches overnight. Nitrosamines were not detected in any of the ambient air samples nor in the untreated well and river water samples. In the grab sample * collected from the treated wastewater effluent, 13 pg/l dipropylnitro- samine (DPN) was detected, and confirmed by mass spectral analysis. This amine probably originated in the process making Oryzalin. At this low level concentration, DPN would not be detected in the Catawba River. PROCTOR CHEMICAL COMPANY, INC . In 1938, the Proctor Chemical Company was founded by Edward C. Proctor. The Company became the wholly owned subsidiary of National Starch and Chemical Corporation, Inc. in 1969. The Company manufactures almost every chemical compound used in the textile industry, except for * Detection limit — 0.2 pg/i. ------- 19 Table 2 MONITORING SITE DESCRIPTION MARTIN-MARIETTA CORP. Charlotte, North Carolina Sample Description Site Location Untreated river water Intake Dump house, from the fish bioassay feed line Untreated well water Water fountain in Sales Service Building Treated wastewater effluent Canal, approximately 0.54 km (0.33 mile) downstream from the final settling lagoon, about 9 m (30 ft) upstream from confluence with river Air - north site Roof of building 11, analytical laboratory. About 45 to 60 m (150 to 200 ft) from ñighway 27 (downwind site) Air - wètt site Intake pump house, about 91 m (100 yd) downstream from highway 27 bridge; on intake pipe superstructure dock, about 3 m (10 ft) west of stairs on dock (qround or dock level) Air - south site West side of preaeration nond on SW side of oond.’ Upwind site (ground level) Air - northeast site About 30 rn (100 ft) south of spur railroad tracks, behind bldg. 39 (ground level) ------- E J 2 FIGURE 4 MARTIN MARIETTA CORPORATION SODYECO DIVISION CHARLOTTE, N. CAROLINA GENERAL PLANT LAYOUT • AIR MONITORING SITE N t . N) S ------- 21 dye stuffs, and produces over 500 products in varied lot sizes from 55-gallon drums to tank truck and railroad car bulk quantities. Proctor Chemical has the capability to produce almost any chemical formulation to a customer’s specification. The plant also produces custom chemicals for larger chemical companies which do not want to invest capital for new processes. About 40% of their products are manufactured for other companies. Proctor Chemical Company consists of two plants, situated approxi- mately 8 kin (5 mi) apart. The Lumber Street Plant [ Figure 5] consists of 4,600 m 2 (49,000 ft 2 ) of manufacturing, warehousing, shipping and main offices while the new (1971) Cedar Springs Plant [ Figure 6] consists of 5,000 m 2 (53,600 ft 2 ) of manufacturing and warehousing. The Cedar Springs Plant is located on 16 ha (40 acres) in the rural area of Salisbury while the Lumber Street facility is within the City limits and bounded on all sides by other businesses. Both facilities operateS 5 days/week, 24 hr/day. Water Supply and Wastewater Treatment All water used at both plants is purchased from the City. Fresh water used for condensers and reactors is recycled through cooling towers; there are three towers at the Lumber Street Plant and one tower at Cedar Springs. Sanitary wastewater from the Lumber Street facility is discharged directly to the municipal wastewater treatment plant. Sanitary waste- water is discharged to a septic tank and leach field at the Cedar Springs Plant. Process wastewater is not discharged from either plant to receiving waters. At the Lumber Street Plant, all wastewaters, clean-up waters, ------- 22 AIR MONITORING SITE. S A LARGE REACTORS (OVER 2 GAL) [ ] ( ) B SMALL REACTORS (UNDER 2 GAL) C DISTILLAIION o STOR*GE (MIXING O.EANJNG fTl ® In F CEP4TRIR CE LW G OR RS— H PILOT REACTORS C S STEAk) BOtLERS(t6O C) J NOTOLBOILERSI3 °C t:) R REFRIGERATION COOLING C7 U WASTE TREATMENT I CE) I . COOLING (_7 N FIRE PROTECTION o TRUCJc CALES P ION EXOIANGE £ o ORUMFLAJCER LA 2.GIa (g LA LA tj a, I a- 1.1 LA •Soh nI R .erp U F ictO lcli — V Arfl w d Fluid Bid 49.406 SQ. Ft 1j®EJ FIGURE 5 PROCTOR CHEMICAL COMPANY, INC. SALISBURY, N. CAROLINA LUMBER STREET PLANT GENERAL PLANT LAYOUT 5PcQ 4IOU CEXE)®e o7 ( ® ------- • AIR MONITORING SITE ‘Jr 53.590 SO. FT. R LLR ROOM ElElEI ill 00 0 000 00 O Mu1 0 0 i 1 0 T ’J 0 0 0 0 0 e IO( TAla T GI 00 0 ACT SC SC TIR ROOM 0 OJT$JDE TM I ETOR I A LARGE REACTORS (OVER 2 GAU o SMAU. REACTORS (UNDER 2XOGM ) C D ISTIU .AT1ON o STORAGE E MIXING F CENTRIFUGE 6 DRYERS H PILOT REACTORS I S E.AM BOILERS(1SCRC) J HOT OIL BOILERS (3 K REFRIGERATION COOUE4 L C ING M WASTE TREATMENT N PIPE PROTECTION SYSTEM O TRUOXSCA(.ES p ION EXO4ANGE 0 DRUM FLANER 1 Su ES 2GIau MISC 4-LaRd M • p4 RacC 4fy ld Ffi aRd TalAlly Br d VRQAJP FkRd Bud FIGURE 6 PROCTOR CHEMICAL COMPANY, INC. SALISBURY, N. CAROLINA CEDAR SPRINGS PLANT GENERAL PLANT LAYOUT . ullunu El El Of CE M O OIJA&ITY nRCLL 4a A To 4 C. C. C® ‘LI . 00 0lo I ------- 24 rainwater, cooling tower and boiler bleedoff are discharged to the municipal wastewater treatment facility. Prior to discharge to the municipal sewer, the wastewaters flow to two 530 m 3 (140,000 gal) ca- pacity tanks, operated in parallel; the wastewaters are aerated with surface aerators. The flow averages 380 liters/mm (100 gpm). The two aeration tanks are located above ground and are open to the atmosphere. A portion of the wastewater flows through a 76 m 3 (20,000 gal) under- ground holding tank located in the drum cleaning area, before discharge to the two surface tanks. Process wastewaters are not discharged from the Cedar Springs facility. All wastewaters drain to two settling and separation pits, each about 3 m square x 0.9 m deep (10 ft square x 3 ft deep), operated in series. Material is either recovered from the pits or pumped to one of two unlined lagoons, operated in parallel. There are actually three lagoons; however, one does not receive plant wastewater, and contains storm water runoff. The wastewaters in the two lagoons are continually recycled through spray nozzles into the air to assist in evaporation. There is no known discharge from either lagoon. Six wells, ranging in depth from 6 to 12 m (20 to 40 ft) deep, are used for monitoring on the Cedar Springs property to determine if the wastewater from the lagoons is seeping into the ground water. The wells are monitored weekly for pH, manganese, chloride, COD, total hardness, total solids, and total volatile solids; to date the data has not indi- cated that the wastewater is entering the ground water. Processes The total production capacity of both plants is 27 million kg (60 million lb)/yr. Originally, the Company sulfonated animal oils and fats for the textile industry; however, the chemical formulations for textiles ------- 25 have grown to include dye auxiliaries, thermosetting resins, wetting agents, etc. Formulations include concentrates, fluids, flakes, small chunks, and waxy materials. All processes are operated on a batch basis using stainless steel, glass—lined steel, or lead-lined reactors. In addition, specialized systems such as distillation columns and enclosed centrifuge and solids handling equipment are available for formulations with specialized requirements. Units processes include: Al coholysis Al kyl ation Am i dat i on Crystall ization Distillation Esterification Flaking Hydrolysis Oxidation Phosphation Product categories include: Antistatic Agents Antistick Agents Catalyst Detergents Dye Assistants Dye Fixatives Emul sifiers Flame Retardants Lubricants for Yarn Propoxyl ation Reduction Sulfonation (O°-230°C) Vacuum Drying Chlorination Quaterni zation Organometal 1 ic Condensation Etheri fi cation Sul fation Reactants Resins Sanforizing Agents Scouring Agents Softeners Sulforiated Fats and Oils Weighers Wetting Agents Due to the large number of batch processes available at Proctor Chemical, detailed process evaluations were not conducted. However, typical process descriptions for reactions using amines fall into three categories. 1 . Diethanol Amine Reaction [ Figure 7-A] - This process is located at the Lumber Street facility only, in the synthetic area. The only source of amines would be to the atmosphere as there is no wastewater discharge. The air emissions are not controlled. ------- 26 EJ 4vff 0z 1• + _t, p P .AIN J TO A TiOI4 TAP&I(S I- 9 AMiO P O c. ’lDN Sc Ru8 4 1 _ 1 , PHO PMORiC ACID TO I-AGOOH PLUMS; 40 lb C.AeT0 JS) ea om R AcTjON FIGURE 7 PROCTOR CHEMICAL COMPANY, INC. SALISBURY, N. CAROLINA TYPICAL AMINE REACTION SEQUENCES A. p ETl4p.NOLAMpr aE R A 1ION C. Tt%METI$TLAMIN . R . craoH ------- 27 2. Amide Production [ Figure 7—B] - This process is conducted at both plants. Air emissions are vented through a shell and tube conden- ser; condensables are discharged to the wastewater system while non-conden- sables are vented to the atmosphere. 3. Trimethylamine Reaction [ Figure 7-C] - Air emissions from the reactor are vented to a shell and tube condenser and then to a counter- current fume scrubber, packed with ben saddles. Phosphoric acid solu- tion cascades through the scrubber from the top. About 180 kg (400 lb) of acid, mixed with 1,500 liters (400 gal) of water; is used each day. The spent scrubbing solution is discharged to the lagoon system. This process is used only at the Cedar Springs Plant. The raw and intermediate materials used in the processes were pro- vided to NEIC, however, Company personnel consider these materials pro- prietary and requested that they not be identified in the report. Monitoring Results Monitoring was conducted on May 3, 1977; a description of the air and water monitoring sites for both plants is given in Tables 3 and 4, and shown in Figures 5 and 6. The air speed varied between 6 and 15 km (4 and 9 mi)/hr and was out of the southwest. The temperature during the monitoring period was between 75° and 80°F; sky conditions were partly cloudy. Nitrosamines were not detected in the ambient air samples at either process facility nor in any water/wastewater sample from the Lumber * Street Plant. A concentration of 0.1 pg/l of dimethylnitrosamine (DMN) was detected in the municipal water supply sample at the Cedar Springs * Detection limit = 0.2 pg/i. ------- 28 Table 3 MONITORING SITE DES CRTh’ TION PROCTOR CHEMICAL COMPANY LUMBER STREET PLANT Salisbury., North Carolina Sample Description Site Location Municipal water supoly Main office building, sink in men’s roon Process wastewater effluent Valve from aeration tank after 24 hr of aeration closest to the research building, farthest from nlant (filled 5-2-77) Process wastewater effluent Valve from aeration tank before aeration to the plant (being filled on 5-3-77) Air - south of processes, Inside of fence line, upwind of site approximately 0.6 m (2 ft) off of Lumber Street, about 6 m (20 ft) west of alley entrance (Unit on top of 55 gal. drum) Air - west of orocesses 38 to 46 m (125 to 150 ft) downwind of the two aerated storage tanks, about 3 m (10 ft) in ide of fence line (unit elevated about 2 m (7 ft) off of ciround) Air - northeast of processes, !lortheasternmost section of downwind of site plant, adjacent to drum cleaninq facility (unit elevated about 6 m (20 ft) above ground) Air - east of processes On N 1 corner roof of Lower Warehouse ------- 29 Table 4 MONITORING SITE DESCRIPTION PROCTOR CHEMICAL COMPANY, INC. CEDAR SPRINGS PLANT Salisbury, North Carolina Sample Description Site Location Municipal water supply Fresh water intake at burner shed sniciot, adjacent to lagoons Process wastewater, untreated From second settling and separation pit (closest to lagoons) Process wastewater from east About 7.6 rn (25 ft) east of lagoon puma house on west side of lagoon #1 Process wastewater from middle From middle of lagoon #2 lagoon (lagoon almost dry) Grant’s Creek Creek as it leaves north side of property, about 30 m (100 ft) off property at bridge Air — south of processes, Midway between settling upwind site and separation Dits and lagoons near east end of lagoon #1 (unit on 55 gal. drum) Air - east of processes ApDroximately 15 m (50 ft) north of scale house, about 4.6 m (15 ft) east of road (unit at ground level) Air — north of processes Between ammonia burner and 1ant building, about 12 m (40 ft) north of building across road (unit at ground level) Air - west or processes On tank truck ramp (unit at ground level) ------- 30 Plant, but was not detected in any of the process wastewater samples, nor in the Grant’s Creek sample. Also, DMN was not detected in the municipal water supply at the Lumber Street Plant, and both fresh water supplies are from the Salisbury utility. Therefore, DMN was most probably not present in the sample, but was detected due to the solvents used in * extraction. Nitrosaniines were not detected in the Grant’s Creek sample nor in the sample collected from the middle lagoon (lagoon #2); this lagoon ** was almost dry. However, 8.2 pg/i propylbutylnitrosamine (PBN) and 3.2 pg/i PBN were detected in the wastewater effluent from the settling and separation pit (influent to lagoon #1) and in the sample collected from lagoon #1), respectively. The PBN could not be confirmed by GC/MS at the levels detected due to a masking effect by a large number of components at higher concentrations. Although a number of occurrences of prominent PBN masses were found, the spectra of those peaks were not PBN. Of the amines used at the plant, the precursor of PBN was not in the inventory. VELSICOL CHEMICAL COMPANY Velsicol Chemical Company operates two plants at Chattanooga. These are designated as the Semi—works and Main Plant, located across the - street from each other. Water Supply and Wastewater Treatment Fresh water for both plants is supplied by the City of Chattanooga. The amount of water was not provided during the NEIC inspection. * The solvents used in NEIC’s extraction method produces peaks that appear similar to DMN and nitrosomorpho line in the presence of residual chlorine. ** Detection limit = 0.2 pg/i. ------- 31 Sanitary wastewaters from both plants are discharged to the municipal sewer system. Process wastewater, water used to clean reaction vessels, mix tanks, etc., from the Semi-works are discharged into a holding tank. After neutralization, the wastewaters are discharged to the municipal sewer system. Sediments from the holding tank are landfilled. If the process wastewater contains materials such as toluene, the wastewater is discharged into drums and hauled away for incineration by a private contractor. Process wastewater and wastewaters from air scrubber systems at the Main Plant are discharged to the City sewer. The waste- waters are pretreated; however, the Company considers the treatment to be confidential. At the time of the survey, the sewer was being re- placed because the wastewater had apparently dissolved the pipe. Storniwater and seepage from the north side of the Main Plant are discharged to the Tennessee River via a drainage ditch. Processes The Semi-works develops new products through research and also manufactures some specialty products. These products include esters of berizoic acid, dicyclopentadiene, methendic alcohol, dimethylchlorperitacine, dimethylchlorendate, and sucrose benzoate. One product, designated as * MAADMA contains amine compounds. The majority of the processes are conducted on a batch basis in 1.9 m 3 (500 gal) vessels. Other equipment use consists of stills, autoclaves, neutralization tanks, and mix tanks. The Main Plant produces benzoic acid, benzoic acid esters, benzo nitrile, benzo guanamine, benzo alcohol, benzo trichioride, benzoyl * Chemical name is considered confidential. ------- 32 chloride, benzoyl alcohol, and similar chemicals. Production figures are considered confidential. Process vapors in the Semi-works plant are normally returned to the reaction vessel. However, some vapors, including fugitive, are vented to the atmosphere. Air pollution control at the Main plant is by means of scrubbers. The Company indicated however, nitrogen is emitted to the atmosphere from the benzoic acid process. They indicated that stack tests have been conducted at the Main Plant to determine if manufactured compounds were being emitted. The results were not avail- able at the time of the NEIC survey. Monitoring Results A description of the air and water monitoring sites for both plants is given in Table 5. The air speed ranged between 4.8 and 11 km (3 and 7 mi)/hr and varied in direction. The temperature was about 80°F. N—nitroso compounds were not detected in the ambient air, water or wastewater samples. FARMERS SUPPLY AND PRODUCE Farmers Supply and Produce, a retail store, supplies hardware, feed, seed, fertilizer, pesticides and herbicides to the general public. The pesticides and herbicides are purchased pre-packaged and are either sold as-received or mixed with liquid nitrogen or dry fertilizer. On an average basis, the store sells about 2,700 kg (6,000 lb)/yr of pesti- cides and herbicides with only 900 kg (2,000 ib) being pre-mixed at the store with fertilizers. The amount of these compounds sold in 1976 are as follows: ------- 33 Table 5 MONITORING SITE DESCRIPTION TTELSICOL CHEMICAL COMPANY Chattanooga, Tennessee Sample Description Site Location Semi -Works Air - south of processes Air - west of processes Air - north of processes Air - east of processes At fence line At fence line At fence line Roof of office building Main Plant City water supply Process wastewater after pretreatment Runoff Air - south of processes Air - west of processes Air - north of processes Air - east of processes Main office building Discharge to the municipal sewer North side of plant South side of plant At fence line next to office building At fence line adjacent to Coke Plant East side of plant near wastewater discharge to sewer ------- 34 Liquid atrazine 300 1 (80 gal) Atrex 80 W 900 kg (2,000 ib) Paraquat 380 1 (100 gal) Lorax 90 kg (200 lb) Balan 450 1 (120 gal) Princep 80W 110 kg (250 gal) At the time of NEIC’s inspection, atrazine powder (Atrex 80W) was being mixed in water and added to ammonia. Mixing is conducted outside; only a very small amount of dust was lost during mixing due to the care taken by employees. The total mixing time takes less than 5 minutes; the number of batches varies daily, depending on customer orders. Water is only used for mixing of the compounds; the operation does not have any process discharge. Empty chemical containers are placed in trash containers and removed by a contractor. Due to the limited amount of materials being used and the nature of the operation, ambient air and water samples were not collected. ------- IV. SUMMARY AND CONCLUSIONS Ambient air and water samples were collected at four industrial facilities and analyzed for N—nitroso compounds. Farmers Supoly and Produce, a retail store, was not sampled. Except for one sample collected at the Ciba-Geigy Corporation plant at McIntosh, Alabama, N—nitroso compounds were not detected in the ambient air samples. The wind direction during monitoring at Ciba-Geigy was variable, but mainly from the southwest. About 40 ng/m 3 of dimethylnitrosamine (DMN) was detected in the upwind monitoring site sample. This concentration is in the range found at Baltimore, Md., and Belle, W. Va. Olin Chemical is located south (upwind) of Ciba-Geigy’s property and has nitrating facilities. However, whether the DMN originated from Olin Chemical, or Ciba-Geigy, is unknown. Based on one positive sample, it cannot be concluded that nitrosamines are present at low levels or are ubiquitous in the plant’s environment. The negative results indicate that 1) nitrosamines are not emitted, 2) nitrosamines were not emitted durinq sampling, 3) once in the atmosphere the N-nitroso compounds decomposed rapidly, or 4) the compounds were not collected by the sample train due to environmental conditions. DMN’s presence indicates some deoree of risk and Ciba-Geigy should eliminate the emission. The Company has the capability to monitor and analyze nitrosamines. Water samples collected from Ciba-Geigy Corporation, ? artin-Marietta (SODYECO), and Proctor Chemical Comoany indicate that there are primary sources of direct emissions to the environment of a number of M-nitroso compounds. The compounds probably arise as impurities during the synthesis of other compounds and are emitted to the environment during the use or modification of these products. The source and types of nitrosamines detected are as follows: ------- 36 Conc. Facility Sample Description ugh N-Mitroso Compound Ciba-Geigy Treated wastewater effluent 0.05 Dimethylnitrosamine 0.63 Nitrosopyrrolidine Martin-F•larietta Treated wastewater effluent 13.0 Dipropylnitrosamine Proctor Chemical’s Cedar Springs Plant City water 0.1 Dimethylnitrosamine Process wastewater influent to Propylbutylnitros- evaporation lagoon 8.2 amine* Wastewater in Propylbutylnitros- evaporation lagoon 3.2 amine* * PBN could not be confirmed by CC/MS due to macking by the Zarge number of components at higher concentrations and because a PBN standard zx s not availcbl-e at a high enough concentration to measure the exact retention time and detection limits by CC/MS. In-plant sampling would be required to locate the sources of these compounds; however, at th levels observed, it is doubtful that this effort would be useful expenditure of EPA’s resources. There is a lack of data indicating the level at which health’ effects are observed and what these effects are. One cannot safely speculate as to the significance of the numbers ‘or the population at risk. Where these compounds are discharged into waterways, it is possible that they may find their way into drinking water supplies. This has been routinely demonstrated with other compounds. Where health effects data are lacking, the safest posture is to assume no threshold level exists, and to minimize the environmental impact of known carcinogens wherever possible.’ ------- 37 REFERENCES 1. “Reconnaissance of Environmental Levels of Nitrosamines in the Central United States,” EPA Office of Enforcement, National Enforce- ment Investigations Center, Denver, Colorado, January 1977, EPA- 330/1 -77-001. 2. Fine, D. H., Rounbehiet-, D. P., Beicher, N. M., Epstein, S. S., “International Conference on Environmental Sensing and / ssessment,” Catalogue #75-CH 1004-1 ILESA, pp. 30—7, IEEE, New York, New York, 1976. 3. Fine, D. H., Rounbehier, 0. P., Beicher, N. M., Epstein, S. S., SCIENCE , 192, 1328 (1976). ------- APPENDIX A NEIC ANALYTICAL PROCEDURE FOR NITROSAMINES ------- NEIC ANALYTICAL PROCEDURE FOR NITROSAMINES Air Samples Air samples were collected in foil-covered imDinQers (S(A catalog #JV8550) filled with 60 ml of lN KOH. Air samples were drawn through the impinger by a vacuum pump and the flows controlled by a calibrated stainless steel hypodermic needle (B&D 1 /21). Normal collection volumes ranged from 200 to 250 liters of air per needle. Dual impinaers were used to collect samples at each monitoring locations. The two samoles were combined in the NEIC Laboratory prior to analysis. All laboratory work was carried out under low UV “bug” lights to minimize the possibility of light catalyzed degradation of the nitro- samines. The KOH solutions were extracted in a 250 ml separatory funnel with three 8 ml portions of dichloremethane (Burdick and Jackson, “distilled in glass”). The combined extracts were concentrated to 0.5 ml in Kuderna-Danish evaporative concentrators, each consisting of a three-ball Snyder column attached to a specially made 50 ml concentrator flask which in turn was attached to a 4 -ml calibrated receiving tube. The column and receiving tube are available through Kontes ‘ lass Company; the 50-mi flask was custom made locally. Before concentration, 0.5 ml of 2,2,4 trimethylpentane was added as a keeoer. A hot water bath maintained at 59 to 60°C was used as the heat source. Microliter aliquots of the concentrates were injected into a Varian Model 600D gas chromatograph attached to a modified Thermal Energy Analyzer (GC/TEA). An n—propanoi/liquid nitrogen cold trao was used in conjunction with the modified TEA. ------- Where possible, samples thought to contain nitrosarnines were spiked with known standards to confirm retention time and to help establish concentrations. P 10% Carbowax 20M, 1% KOH on 60/80 n’esh Chromosorb WAW, column was employed for analysis. The retention time of the sample peaks matched those of the standard solutions of nitrosamines. Quantitation of compounds reported was made by peak height comparison with authentic standards, obtained through the Food and Drug Administration, Washington, D.C. Water Samples Grab samples were collected in amber glass 0.946 liter (quart) bottles with Teflon liners. Two 50-mi portions of dichioromethane were used to extract each sample in a 2,000-ml separatory funnel. The combined extracts were concentrated as above, only using a 250—mi concentrator - flask and 1 nil of 2,2,4 trimethylpentane as a keeper. Volumes injected into the GC/TEA were kent as small as possible. Granular anhydrous sodium sulfate (Mallinkrodt AR) was used to treat emulsions when they occurred during extractions. ------- QUALITY CONTROL During these studies, the following quality control considerations were evaluated: Solvent Blanks Methylene chloride (dichioromethane) was concentrated from at least three different bottles from 100 ml to 1 ml using an isoctane keeper and was found to contain no peaks which specifically interfere with the analyses. Similarly, unconcentrated Burdick and Jackson methylene chloride and isoctane were analyzed with the GC/TEA system and found to be free from interferences. Nitrosamines Free Water Nitrosamine free water was taken to the field and used to prepare the 1 N KOH solution for the impingers. Twenty to fifty ml of the nitrosamine free water was used to wash each impinger sample into sample containers. The sample bottles were capped (caps had Teflon liners) and were sealed with electrician’s tape. The riitrosamine free water was analyzed in the NEIC laboratory to confirm the absence of N-nitroso compounds. Extraction Efficiencies Quart samples of water were spiked with DMN, DEN (diethyl-N-nitrosamine) and DBN (dibutyl-N-nitrosamine), extracted and concentrated in the normal manner to determine recovery from water samples. The average recoveries ------- were as follows: DMN 32%, DEN 87%, and DBN 96%. The addition of NaC1 to increase recovery during water extractions was studied but found ineffective. Overall collection and extraction efficiency was determined for air samples by passing known quantities of dimethyl—N-nitrosamine, ethylrnethyl-N-nitrosamifle, diethyl—N-nitrosamine, dipropyl—N-nitrosamine, ethylbutyl-N-nitrosamine, nitrosopyrrolidine, and nitrosomorpholine through KOH impingers at ambient temperatures of -2°C and 20°C, then extracting and concentrating as usual. For these compounds, the average recovery at -2°C was 65% and at 20°C, 78%. There were no apparent differences in efficiencies between the various compounds examined. ------- APPENDIX B SAMPLE VOLUMES ------- APPENDIX B SAMPLE VOLUMES April—Play, 1977 Location Station Description and Date Sample Sample Type Volume ( liters ) Ciba-Geigy Untreated well water 5/25 0.946 Treated well water 5/25 0.946 Untreated river water 5/25 0.946 Treated river water 5/25 0.946 Treated wastewater 5/25 0.946 South site--air 5/25 471.6 East site--air 5/25 471.6 North site--air 5/25 478.8 West site--air 5/25 484.8 Martin Marietta Untreated river water 5/5 0.946 Well water 5/5 0.946 Treated wastewater 5/5 0.946 North site--air 5/5 462.6 West site--air 5/5 477.0 South site--air 5/5 467.4 Northeast site-—air 5/5 505.8 Proctor Chemical Lumber Street Municipal water 5/3 0.946 Wastewater after aeration 5/3 0.946 Wastewater before aeration 5/3 0.946 South site--air 5/3 62.6 West site—-air 5/3 477.0 Northeast site--air 5/3 467.4 East site—-air 5/3 505.8 Cedar Springs Municipal water 5/3 0.946 Untreated wastewater 5/3 0.946 Wastewater--east lagoon 5/3 0.946 Wastewater--middle lagoon 5/3 0.946 Grant’s Creek water 5/3 0.946 South site--air 5/3 462.6 East site--air 5/3 477.0 North site—-air 5/3 467.4 West site—-air 5/3 505.8 Velsicol Semi—works South site--air 4/19 434.1 West site--air 4/19 565.8 North site--air 4/19 572.5 East site—-air 4/19 494.1 ham Plant Runoff water-north 4/19 2.0 Wastewater 4/19 2.0 City water 4/20 2.0 South site--air 4/20 465.6 North site--air 4/20 491.5 West site-—air 4/20 524.4 East site-—air 4/20 471.1 ------- |