United States Environmental Protection Agency Industrial Environmental Research Laboratory Cincinnati OH 45268 EPA-600/2-78-004g April 1978 Research and Development Source Assessment: Rail Tank Car, Tank Truck, and Drum Cleaning, State of the Art Environmental Protection Technology Series ------- RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into nine series. These nine broad cate- gories were established to facilitate further development and application of en- vironmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The nine series are: 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies 6. Scientific and Technical Assessment Reports (STAR) 7 Interagency Energy-Environment Research and Development 8. "Special" Reports 9. Miscellaneous Reports This report has been assigned to the ENVIRONMENTAL PROTECTION TECH- NOLOGY series. This series describes research performed to develop and dem- onstrate instrumentation, equipment, and methodology to repair or prevent en- vironmental degradation from point and non-point sources of pollution. This work provides the new or improved technology required for the control and treatment of pollution sources to meet environmental quality standards. This document is available to the public through the National Technical Informa- tion Service, Springfield, Virginia 22161. ------- EPA-600/2-78-004g April 1978 SOURCE ASSESSMENT: RAIL TANK CAR, TANK TRUCK, AND DRUM CLEANING State of the Art by D. E. Earley, K. M. Tackett, and T. R. Blackwood Monsanto Research Corporation Dayton, Ohio 45407 Contract No. 68-02-1874 Project Officer Ronald J. Turner Industrial Pollution Control Division Industrial Environmental Research Laboratory Cincinnati, Ohio 45268 INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY CINCINNATI, OHIO 45268 ------- DISCLAIMER This report has been reviewed by the Industrial Environmental Research Laboratory-Cincinnati, U.S. Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the U.S. Environmental Protection Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use. ------- FOREWORD When energy and material resources are extracted, processed, converted, and used, the related pollutional impacts on our environment and even on our health often require that new and increasingly more efficient pollution control methods be used. The Industrial Environmental Research Laboratory - Cincinnati (lERL-Ci) assists in developing and demonstrating new and improved methodologies that will meet these needs both effici- ently and economically. This report contains an assessment of air emissions and water pollutants from the rail tank car, tank truck, and drum cleaning industry. This study was conducted to provide a better under- standing of the distribution and characteristics of pollutants from this industry. Further information on this subject may be obtained from the Organic Chemicals and Products Branch, Indus- trial Pollution Control Division. David G. Stephan Director Industrial Environmental Research Laboratory Cincinnati 111 ------- PREFACE The Industrial Environmental Research Laboratory (IERL) of the U.S. Environmental Protection Agency (EPA) has the responsibility for insuring that pollution control technology is available for stationary sources to meet requirements of the Clean Air Act, the Federal Water Pollution Control Act, and solid waste legislation. If control technology is unavailable, inadequate, or uneconomi- cal, financial support is provided for the development of control techniques needed for industrial and extractive process indus- tries. Approaches considered include process modifications, feedstock modifications, add-on control devices, and complete process substitution. The scale of the control technology pro- grams ranges from bench- to full-scale demonstration plants. IERL has the responsibility for developing control technology for a large number (>500) of operations in the chemical and related industries. As in any technical program, identifying the un- solved problems is the first step. Each industry is to be exa- mined in detail to determine if there is sufficient potential environmental risk to justify the development of control tech- nology by IERL. Monsanto Research Corporation (MRC) has contracted with EPA to investigate the environmental impact of various industries that represent sources of pollutants in accordance with EPA's respon- sibility, as outlined above. Dr. Robert C. Binning serves as MRC Program Manager in this overall program, entitled "Source Assessment," which includes investigating sources in each of four categories: combustion, organic materials, inorganic materials, and open sources. Dr. Dale A. Denny of the Industrial Processes Division at Research Triangle Park serves as EPA Project Officer for this series. Reports prepared in this program are of two types: Source Assessment Documents and State-of-the-Art Reports. Source Assessment Documents contain data on pollutants from specific industries. Such data are gathered from literature, government agencies, and cooperating companies. Sampling and analysis are also performed by the contractor when available information does not adequately characterize the source pollu- tants. These documents contain all the information necessary for IERL to decide whether a need exists to develop additional control technology for specific industries. IV ------- State-of-the-Art Reports include data on pollutants from specific industries which are also gathered from literature, government agencies, and cooperating companies. However, no extensive samp- ling is conducted by the contractor for such industries. Results from such studies are published as State-of-the-Art Reports for potential utility by government, industry, and others having specific needs and interests. This study was undertaken to provide information on air emissions and water pollutants from cleaning rail tank cars, tank trucks, and drums. The work was performed for the Organic Chemicals and Products Branch of the Industrial Pollution Control Division at Cincinnati under Mr. David L. Becker. Mr. Ronald J. Turner of IPCD served as EPA Project Leader. v ------- ABSTRACT This document reviews the state of the art of air emissions and water pollutants from cleaning rail tank cars, tank trucks, and drums. The composition, quantity, and rate of emissions and pollutants are described. Rail tank cars, tank trucks, and drums are used to transport a wide variety of chemical and petroleum commodities from producer to consumer. Steaming, washing and/or flushing of such units result in air emissions and wastewater effluents. Air emissions are predominantly organic chemical vapors. Water pollutants com- mon to these operations are primarily oil and grease, COD, BOD, suspended solids, and many other organic and inorganic materials. Because of the latter, there is a high degree of variability in the wastewater constituents. Representative sources were defined for rail tank car cleaning, tank truck cleaning, and drum clean- ing, the latter with washing and burning and with washing only. To evaluate the hazard potential of the representative sources, source severity was defined and evaluated for air emissions and for wastewater effluents. Control methods used to reduce emis- sions from rail tank car and tank truck cleaning are flaring, absorption, or product recovery of flushed gases. All other emissions are vented. No practical control methods exist for drum washing. Emissions from drum burning furnaces are con- trolled by maintaining proper operating conditions. Wastewater treatments consist of a variety of physical, chemical, and bio- logical processes. By EPA estimates, two-thirds of the tank truck industry discharges to municipal systems with little or no pretreatment. Where it has been provided, treatment has general- ly been limited to sedimentation, neutralization, evaporation ponds, and lagoons. This report was submitted in partial fulfillment of Contract No.- 68-02-1874 by Monsanto Research Corporation under the sponsor- ship of the U.S. Environmental Protection Agency. This report covers the period August 1976 to June 1977, and the work was completed as of September 1977. VI ------- CONTENTS Foreword . iii Preface iv Abstract vi Tables viii Abbreviations and Symbols x Conversion Factors and Metric Prefixes xi 1. Introduction 1 2. Summary 2 3. Source Description 7 Cleaning operations description 7 Geographical distribution 16 4. Emissions 21 Selected pollutants and emissions 21 Definitions of representative sources 25 Environmental effects of air emissions 26 Environmental effects of water pollutants .... 29 5. Control Technology 38 Present technology 38 Future considerations 46 6. Growth Potential 47 References 48 Appendices A. Estimates of drum burning emissions 51 B. Definition of source severity for water discharges and calculation of river or end-of-pipe concentrations . 53 Glossary 55 vxi ------- TABLES Number Page Water Pollutants from Rail Tank Cars, Tank Trucks, and Drums 2 Source Severities for Air Emissions from a Represen- tative Cleaning Source for Rail Tank Cars, Tank Trucks, and Drums . . . 4 3 Source Severities for Water Pollutants from a Repre- sentative Cleaning Source for Rail Tank Cars, Tank Trucks, and Drums 5 4 Tank Car Cleaning Facilities Data 10 5 Products Handled and Percent of Total Haulage 12 6 Trailer Internal Cleaning Generation Rates for One Terminal During One Month of Operation 12 7 Commodity/Tank Truck Data for One Terminal During One Month of Operation 13 8 Production of Steel Drums 15 9 Rail Car Cleaning by State 17 10 Tank Truck Cleaning by State 19 11 NBADA Member Drum Cleaning and Burning by State .... 20 12 Measured Emissions from Tank Car and Tank Truck Cleaning 22 13 Waste Treatment Plant Effluent Data, June 1973 .... 23 14 Treatment Plant Operating Results—Matlack, Inc., Swedesboro, New Jersey 24 15 Maximum Ground Level Concentrations and Severity Factors for Different Emissions 28 Vlll ------- TABLES (continued) Number Page 16 Mass of Emissions from Tank Truck and Rail Tank Car Cleaning and Comparison with State and National Hydrocarbon Emission Burdens 30 17 Mass of Emissions from Drum Burning and Comparisons with State and National Particulate Emission Burdens 32 18 Effluent Concentrations and Hazard Factors for Representative Soruces 34 19 Source Severities for Representative Sources 34 20 Rail Tank Car Cleaning Contributions to State Emission Burdens 35 21 Tank Truck Cleaning Contributions to State Emission Burdens 36 22 Drum Washing Contribution to State Emission Burdens . . 37 23 Lowest Effluent Concentrations Expected Using Various Treatment Process Combinations for Petroleum Refineries 45 IX ------- ABBREVIATIONS AND SYMBOLS AAQS — ambient air quality standard BOD — biochemical oxygen demand BODs — amount of dissolved oxygen 'consumed in five days by biological processes breaking down organic matter in an effluent C — exposure level concentration CD -- raw effluent concentration CM — combustible material COD — chemical oxygen demand Cc — saturated dissolved oxygen concentration at 10°C o (DO)WQ_, — dissolved oxygen fresh water quality criteria e -- 2.72 F — hazard factor H -- emission height LC50 — lethal concentration of a pollutant to 50% of an aquatic life exposed to the pollutant LD50 — lethal dose of a pollutant to 50% of a male rat population pH — measure of acidity or alkalinity of a material Q -- mass emission rate S — source severity -- severity of total oxygen demand potential TOD — total effluent oxygen demand TSS — total suspended solids TLV — threshold limit value u~ -- average wind speed Vn -- volumetric flow rate of discharge Vn — volumetric flow rate of receiving waters K VSS — volatile suspended solids Y — maximum ground level concentration of pollutant Amax ^ ^ -- time-averaged maximum ground level concentration of pollutant — 3.14 ------- CONVERSION FACTORS AND METRIC PREFIXES CONVERSION FACTORS To convert from Degree Celsius (°C) Gr am/me te r 3 (g/m 3) Gram/second (g/s) Kilogram (kg) Kilogram/meter 3 Meter (m) Meter/second Meter3 (m3) Meter3 (m3) Meter3 (m3) Meter3 (m3) Meter3/second (m3/s) Metric ton Milligram/liter (mg/£) Pascal (Pa) Pascal (Pa) Second (s) To (kg/m3) (m/s) Degree Fahrenheit (°F) Pound/gallon Pound/hour Pound-mass (pound mass avoirdupois) Pound/gallon Foot Foot/minute Barrel (42 gallon) Foot3 Gallon (U.S. liquid) Liter (H) GalIon/minute Ton (short, 2,000 pound mass) Pound/gallon Torr (mm Hg, 0°C) Pounds-force/in.2 (psi) Minute Multiply by t° = 1.8 t° + 32 8.344 x 10~6 7.936 2.205 8.344 x 10~3 3.281 1.181 x 10^ 6.293 3.531 x 101 2.642 x 102 1.000 x 103 1.585 x lO-1* 1.102 8.344 x 10~6 7.501 x 10~3 1.450 x lO'1* 1.667 x 10~2 METRIC PREFIXES Prefix Symbol Multiplication factor Kilo Milli Micro k m y 103 io-3 10~6 Example 1 kPa = 1 x 103 pascals 1 mg = 1 x 10~3 gram 1 ym = 1 x 10~6 meter aStandard for Metric Practice. ANSI/ASTM Designation: E 380-76e, IEEE Std 268-1976, American Society for Testing and Materials, Philadelphia, Pennsylvania, February 1976. 37 pp. XI ------- SECTION 1 INTRODUCTION Various chemical and petroleum products are transported by rail tank cars, tank trucks, and drums. These shipping containers must be cleaned before being used to ship a different material in order to prevent contamination of the new material. Cleaning prior to repair or testing is also necessary. This report presents an assessment of the environmental impact from the cleaning of rail tank cars, tank trucks, and drums which have carried organic chemicals and petroleum products (not in- cluding gasoline, diesel oil, fuel oil, jet fuels, or motor oils). Types of air emissions and wastewater effluents, pollu- tant masses, ground level concentrations, source severities, and affected population are discussed and analyzed. Control tech- nology and the growth of this source are described. ------- SECTION 2 SUMMARY Rail tank cars, tank trucks, and drums are used to transport a wide variety of chemical and petroleum commodities from producer to consumer. Industry officials estimate that as many as 700 different commodities are handled by these carriers. This report does not address such commodities as gasoline, diesel oil, fuel oil, jet fuels or motor oils. Rail tank cars, and most tank trucks and drums, are in dedicated service (carrying one commod- ity only) and, unless contaminated, are cleaned only prior to repair or testing. Nondedicated tank trucks (approximately 20,000 or 22% of the total tank trucks in service) and drums (approximately 5.6 million or 12.5% of the total) are cleaned after every trip to prevent cross contamination. The approxi- mate total number of units cleaned per year are 37,200 rail tank cars, 5,010,000 tank trucks, and 24,680,000 drums. Steaming, washing and/or flushing of rail tank cars, tank trucks, and drums result in air emissions and wastewater effluents. These cleaning operations are partially enclosed. Residual mate- rial is washed to the wastewater stream and only small amounts of material escape through the vents to the atmosphere. Burning of drums (as an alternative cleaning operation) is a more economical cleaning method for large companies but can result in increased air emissions. Air emissions from cleaning of rail tank cars and tank trucks are predominantly organic chemical vapors. If these are all consid- ered as hydrocarbon emissions, the total emissions from each of these industries contribute less than 0.0022% of the national emissions of hydrocarbons. Washing of drums falls into this same class (very low emission of noncriteria pollutants), but some drum burning can produce some criteria pollutants such as hydrocarbons, and nitrogen oxides (NOX). These contribute less than 0.0001% and negligible amounts, respectively, to the national emissions burdens of these pollutants. Water pollut- ants from cleaning of rail tank cars, tank trucks, and drums are primarily oil and grease, total effluent oxygen demand (TOD), suspended solids, and phenol. ------- Since TOD values were not available, they were estimated from the chemical oxygen demand. Quantities of water pollutants from this source in the United States (shown for individual states in Tables 20-22) are summarized in Table 1. TABLE 1. WATER POLLUTANTS FROM RAIL TANK CARS, TANK TRUCKS, AND DRUMS (metric tons/yr) Source type (basis) Oil and grease Suspended solids COD Phenol Rail tank car cleaning (37,220 cars/yr) Tank truck cleaning (5,010,000 trucks/yr) Drum cleaning (24,680,000 drums/yr) 830 1,745 101 4,100 6,070 353 8,300 48,500 2,824 31 986 57 For use in assessing the environmental impact of rail tank cars, tank trucks, and drums used for transporting various chemical and petroleum products, representative sources were defined for each of the cleaning types. A representative rail tank car cleaning station cleans 575 cars per year. The mix of commodi- ties handled is: 35% petroleum products, 20% organic chemicals, 25% inorganic chemicals, 15% compressed gases, and 5% food products. A representative large tank truck cleaning terminal cleans 10,000 tank truck trailers per year. The commodity mix hauled is: 15% petroleum products, 35% organic chemicals, 35% inorganic chemicals, 5% food products, and 10% others (e.g., paints, inks, navel stores, etc.). A representative drum cleaner, washing only, cleans 83,780 drums per year. A representative drum cleaner, washing and burning, cleans 400,000 drums per year, 65% by burning and 35% by washing. To evaluate the hazard potential of the representative sources, the source severity was defined for air emissions and for waste- water effluents. For air emissions, source severity was defined as the ratio of the time-averaged maximum ground level concen- tration of a pollutant emitted from a representative source to a hazard factor, F. For criteria pollutants, the hazard factor is the primary ambient air quality standard; for noncriteria pollutants, it is a "corrected" threshold limit value. For wastewater effluents, the source severity was defined as the ratio of the exposure level concentration to a hazard factor. For oil and grease, phenol, and suspended solids in each of the representative sources, the hazard factor was the EPA fresh water quality criteria for these pollutants. The exposure level concentration was defined as the ratio of the product of the volumetric discharge flow rate and the raw effluent concentra- tion, to the volumetric flow rate of the receiving waters. ------- The source severity of the total oxygen demand potential of a discharge was defined as the ratio of the potential total oxygen deficit to the permissible total oxygen deficit. Total oxygen deficit was based on the discharge water volumetric flow rate, the receiving water volumetric flow rate, and the chemical oxygen demand; the permissible total oxygen deficit was the difference between the saturated dissolved oxygen concentration and the dissolved oxygen fresh water quality criteria. The source severity values calculated for air emissions and waste- water effluents from each type of representative cleaning source are summarized in Tables 2 and 3. i TABLE 2. SOURCE SEVERITIES FOR AIR EMISSIONS FROM A REPRESENTATIVE CLEANING SOURCE FOR RAIL TANK CARS, TANK TRUCKS, AND DRUMS Air Type of cleaning Emissions source severity Rail tank car Tank truck Drum washing Drum burning Ethylene glycol Creosote Chlorobenzene o-Dichlorobenzene Acetone Perchloroethylene Methyl methacrylate Phenol Propylene glycol Organics Particulates Hydrocarbons Carbon monoxide Nitrogen oxide 0.00017a •* U 3.6a'b 0.0061a 0.034a 0.045a O.lla 0.0273 0.100a 0.00143 _C 0.28 P V* _ 0.012 These source severities, due to the intermittent nature of emissions, are for worst case conditions since the maximum ground level concentration was not time averaged. The sample was taken during the first 45 minutes of an 8-hr cleaning operation ; hence the severity value is suspected of being artificially high. Negligible. Unlike most manufacturing industries, the tank truck industry (which is service-oriented) produces wastewater whole volume and characteristics may vary widely at each terminal. Therefore, ------- extensive data would be required for meaningful definition of the raw waste loads generated at truck terminals (1). TABLE 3. SOURCE SEVERITIES FOR WATER POLLUTANTS FROM A REPRESENTATIVE CLEANING SOURCE FOR RAIL TANK CARS, TANK TRUCKS, AND DRUMS9 Type of cleaning Pollutant Water source severity Rail tank car Tank truck Drums (with burning facilities) Drums (washing only) Oil and grease TODb Suspended solids Phenol Oil and grease TOD Suspended solids Phenol Oil and grease TOD Suspended solids Phenol Oil and grease TOD Suspended solids Phenol 0.16 0.0034 0.00033 0.062 0.014 0.00081 0.00002 0.080 0.0094 0.00054 0.000013 0.053 0.0030 0.00017 0.000004 0.017 See Appendix B for detailed explanation of source severity. , Total oxygen demand. The population affected by the average ground level concentra- tion, x", for which x/F>l-0 was determined from the affected area and a representative population density. For emissions from rail tank car and tank'truck cleaning, the affected population is zero. For drum cleaning (both washing and burning), the affected population is also zero. Control methods used to reduce ^emissions from rail tank car and tank truck cleaning are flaring, absorption, or product recovery of the gases flushed from cars or trucks that carry compressed, combustible gases. There are also no practical control methods (1) Analysis of Proposed EPA Effluent Limitations on the For-Hire Tank Truck Industry. National Tank Truck Carriers, Inc., Washington, D.C., June 1974. 31 pp. ------- for emission reduction from drum washing at the present time. Emissions from drum burning furnaces can be controlled by main- taining proper operating conditions. Control technology for the treatment of wastewaters from these cleaning operations consists of increasing use of a variety of physical, chemical, and bio- logical processes. Unless more stringent controls are placed on the cleaning of rail tank cars, tank trucks, and drums, the increase in air emissions from these operations should equal the 30% increase in chemical production which is forecast through 1980. Increased implementa- tion of wastewater treatment processes will lead to an estimated 50% decrease in discharged water pollutants by 1980. ------- SECTION 3 SOURCE DESCRIPTION CLEANING OPERATIONS DESCRIPTION The transportation of organic chemicals from point of production to point of consumption is accomplished in rail tank cars, tank trucks, drums, barges, and pipelines. This report does not cover barge or pipeline transport. Contamination of successive ship- ments can be avoided only by careful cleaning of containers prior to refilling with a different or fresh material. All rail tank cars and most tank trucks and drums are used in dedicated service, which means that they are used repeatedly to transport one kind of material. In this service they are rarely or never cleaned unless they become contaminated. Some materials require periodic cleaning even with dedicated service. For exam- ple, styrene cars and trucks must be cleaned after every fifth trip because of slight polymerization of the styrene building up on the sides of the container (personal communications with F. Bonham, Monsanto Company). Tank trucks and drums not in dedicated service must be cleaned after each trip before another material can be put into them for shipping. These shipping containers must also be cleaned prior to repairs or testing. Rail transportation is the principal mode for long-distance move- ment of bulk chemicals. Truck transportation is used for moving bulk chemicals for distances up to a few hundred miles. Drums are used for transporting smaller quantities of chemicals and are carried by either rail or truck, depending on distance. Rail Tank Car Cleaning There were 177,878 rail tank cars in use in 1972, of which 3,970 were owned by railroads and 173,908 were privately owned. Car owners operating in private carriage of their own products or raw materials (chemical intermediates) account for approximately 10% of the private ownership. The rest are owned by car leasing and operating companies and, along with the railroad-owned cars, are operated on a for-hire basis (2). (2) Yearbook of Railroad Facts, 1973. Association of American > Railroads, Washington, D.C., 1973. ------- Tank car cleaning is conducted largely at shipping and receiving terminals of manufacturers or producers where the wastes are com- patible with and directed to the treatment systems of the indi- vidual companies. However, a significant amount (30% to 40%) of tank car cleaning is carried out at maintenance and service stations operated or contracted by owner-lessors. These instal- lations must clean out wastes derived from a wide variety of commodities, many of which require specific cleaning methods. Wastewaters from these installations are partly or wholly treated on site. The extreme variety of commodities cleaned yields wastewaters which are highly variable, complex, and difficult to treat. A typical tank car cleaning facility cleans from 4 to 10 cars per day. The tank cars cleaned in such facilities are used to haul liquid commodities such as petroleum products (excluding gasoline, fuel oils, and lubricating oils), vegetable and animal oils, organic and inorganic chemicals, beverages, and liquefied gases. Capacity per car varies from 38 m3 to 129 m3 (10,000 gal to 34,000 gal). Cleaning agents used on tank cars are steam, water, detergents, and solvents. These agents are applied using steam hoses, pres- sure wands, or rotating spray heads placed through the opening in the top of the car. Chipping and scraping of hardened or crystallized products is frequently required. Cars carrying gases and volatile materials and those that are being pressure tested have to be filled or flushed out with water. The amount of liquid used per car varies from 0.23 m3 (60 gal) for steam cleaning to 129 m3 (34,000 gal) for total flushing of a large tank car. Table 4 presents tank car cleaning facilities data for several stations (3). The average amount of residual mate- rial cleaned from each car is estimated to be 250 kg (3). Vapors from cleaning cars used to haul volatile materials are sent to flares at some cleaning facilities. Vapors of materials such as anhydrous ammonia and chlorine are dissolved in water and become wastewater constituents. Vapors not flared or dissolved in water are dissipated to the atmosphere. Tank Truck Cleaning An estimated 90,000 tank trucks are in service in the United States, of which 30,000 are used exclusively by the owners to haul their own products and 60,000 are operated on a for-hire basis. (3) Development Document for Proposed Effluent Limitations Guide- lines and New Source Performance Standards for the Railroad Segment of the Transportation Industry Point Source Category. Office of Enforcement and General Counsel, National Field Investigations Center, Cincinnati, Ohio, February 1975. 8 ------- Approximately 20% of the for-hire trucks are used to haul bulk dry freight and 80% are used to haul bulk liquids. Most com- panies operate fleets of five trucks or less; these constitute about 90% of the fleets in operation. The largest operating company has 3,600 trucks in its fleet. Wherever possible, these trucks are consigned to dedicated service, hauling one product for long periods of time. The interiors of dedicated trucks are cleaned infrequently, usually in connection with testing or repair. Interior washing of for-hire tank trucks is conducted at many tank truck dispatch terminals. Each year trucks operating from a single large terminal commonly haul 50 or more organic and inorganic chemicals, salts, acids, bases, agricultural and food products, petroleum products, paint, glue, plastics, soap, lique- fied gas, and latex. Table 5 shows the mix of commodities hauled at a midwest terminal (4). Cleaning tank trucks which have been used for such a wide variety of materials requires great flexi- bility in the selection of cleaning methods. Agents available at most terminals include water, steam, detergents, caustic, acid, and solvents. Tables 6 and 7 show cleaning methods, com- modities and number of tank trucks cleaned at one terminal in one month as supplied by the terminal manager (4). Cleaning agents can be applied with hand-held pressure wands or by Turco or Butterworth rotating spray nozzles. Detergent, caustic, and acid solutions are usually recycled until spent and then sent to the treatment facilities. Solvents are recycled in a closed system, and sludges that accumulate are either incinerated or landfilled. Quantities of liquid used per tank truck vary from approximately 0.23 m3 (60 gal) for steam operations to 20.9 m3 (5,500 gal) for full flushing, with 2 m3 (500 gal) being con- sidered the average. The average amount of material cleaned from each trailer is estimated to be 100 kg (4). * Vapors from volatile materials are flared at a few terminals, but the most common practice is to allow them to dissipate in the atmosphere. Drum Cleaning Steel drums used in shipping organic and inorganic chemicals and other products are manufactured in three categories: 0.2-m3 (55-gal) drums made with 18-gauge steel, 0.2-m3 (55-gal) drums with 20-gauge bodies and 18-gauge heads, and 0.11-m3 (30-gal) drums in 20-/18-gauge. Production of these drums for 1972-1975 is shown in Table 8. (4) Development Document for Proposed Effluent Limitations Guide- lines and Source Performance Standards for the Trucking Segment of the Transportation Industry Point Source Category. Office of Enforcement and General Counsel, National Field Investigations Center, Cincinnati, Ohio, 1975. 9 ------- TABLE 4. TANK CAR CLEANING FACILITIES DATA (3) Cars Site washed/ no . day 118 5.5 119 5.1 120 1.4 121 5.0 122 2.5 123 7 124 11 125 5 126 11 127 4 128 5 129 1.6 130 1.1 131 4.4 132 9 133 9 134 2 Hastewater flow mVday gpd 61 16,000 19 5,000 53 7,000 +7 , 000 tank test water 53 14,000 30 8,000 40 10,600 193 51,000 72 19,000 170 45,000 17 4,500 33 8,600 38 10,000 19 5,000 627 165,600 (includes tank test and cooling water) 95 25,000 {includes sanitary cooling water) 57 15,000 Commodities cleaned Type Oils , greases Acids, bases Solids, foodstuffs Organic liquids Compressed gases Approximately same as above Approximately same as above Approximately same as above Generally same, more vegetable oils, nitrogen fertilizer Organic liquids Inorganic liquids Organic gases Inorganic gases Organic solids Inorganic solids Unknown Same as Site 123 Same as Site 123 Same as Site 123 Same as Site 123 Same as Site 123 Oil Chemicals Compressed gas Food Oil Chemicals Compressed gases Food UPG Anhydrous ammonia Acid and caustic Volatile hydrocarbons Fuel oil and asphalt Food products Unknown Petroleum products Acid and caustic Anhydrous ammonia and LPG Petroleum products Gases Percent of total 29 10 31 13 17 45.5 19.5 4.S 15.5 9.5 0.5 5.0 20.5 38.5 31.2 9.8 32.0 21.3 38.5 8.2 34 19 19 5 11 3 9 60 3 37 90 Cleaning methods Steam, detergent, solvent Dilute with water Hater , steam Steam, water Water purge Same as above but less water due to wanner climate Generally same but higher, lower volume than above Generally same with more solvents (recycled) Generally same as Site 118, but more low pressure high volume water Manual removal of solids; steam; caustic; kerosene; detergent; purging Same as Site 123 Same as Site 123 Same as Site 123 Same as Site 123 Same as Site 123 Steam, caustic Water , detergents , s team Flaring, steam Water, detergent, steam Same as Site 129 Purge steam, water Purge steam, water Neutralise, purge Steam, water, chemicals Purge steam, water, solvent Purge steam, water, solvent Steam, fuel oil, detergent, water Venting, steaming, and detergent Steam , detergents venting Waste treatment Segregation, primary settling; skimming; batch treatment for CK, phenol, CnpH adjust- ment, pond settling Primary settling; oil skimming evaporation; no discharge Collection of excess residual; primary settling; gravity oil separation; equalization pond Primary settling; oil separa- tion in 3 ponds in series Limited collection excess resi- dual; primary settling; gravity oil separation; 3 ponds in series Gravity separation segregation; chemical coagulation; clari- fication Same as Site 123 to city Same as Site 123 to city Pond, no outlet Pond , spray , irrigation ; to city Gravity separation; chemical coagulation; evaporation pond Primary settling; oil separa- tion; to Sanitary District Oil separator; pH adjustment Solvent recycled; landfill fuel oil and asphalt; primary settling skimmer; secondary pond API separatory and closed system; to city Containment and floating skimmers ; evaporation None for tank test water and cooling water to city sewer; closed system and incinera- tion NOTE: Blanks indicate no data reported. (continued) 10 ------- TABLE 4 (continued) (g/m3, for columns listed below) site Oil Suspended solids BODs COD Cyanide Chromium Phenols pH Units no. fax Effluent Raw Effluent Haw Effluent Haw Effluent ten Effluent Haw Effluent Raw Effluent Raw Effluent 118 10-4,000 20-150 50-30,000 15-50 200-40,000 200-5,000 0-1 0-0.02 0-10 0-0.05 0-150 0 1.5-12.5 6.5-8.5 120 much less concentrated than Site 118 in all constituents 121 122 0.24 124 125 126 -» 127 10 128 129 " high _a 252 510 _a _a 835 0.002 7.2 130 21 100 128 0.002 high 131 52.5 23 16 18 11 30 81 135 0.011 0.035 7.5 132 20-645 27-171 50-107 30-49 4.1-4.3 6.3-6.5 133 aito discharge. NOTE: Blanks indicate no data reported. 11 ------- TABLE 5. PRODUCTS HANDLED AND PERCENT OF TOTAL HAULAGE (4) Percent of total hauled Product Rhoplex- latex Glycols Resin Plastics (bulkers) Poly glycols Lacquer Paint and enamel MMA (aery late monomer) Molasses Unidentified Acryloids Toluene Toluenediamine Vinyl acetate Wax Formaldehyde Plasticizers Jet fuel Lube oil Tar Whiskey Miscellaneous 1971 32.5 10.9 10.4 8.1 3.1 1.3 1.2 2.5 5.3 24.5 1972 31.1 21.1 10.6 9.0 4.7 3.0 2.4 2.4 1.7 1.4 1.3 1.1 0.9 0.8 0.8 0.8 0.8 0.8 0.6 0.6 0.5 3.0 NOTE: Blanks indicate these commodities were not cleaned in 1971. TABLE 6. TRAILER INTERNAL CLEANING GENERATION RATES FOR ONE TERMINAL DURING ONE MONTH OF OPERATION (4) Number 1 2 3 4 5 6 7 8 TOTALS Water use, Cleaning method m3/trailer Cold water flush Cold water flush— caustic/acid tank Cold water flush — steam — cold water rinse Cold water flush — spin/detergent — cold water rinse MEK, MIBK / or acetone solvent — cold water rinse Styrene solvent — cold water rinse Cold water flush — steam — cold water rinse — spin w/detergent — cold water rinse Cold water flush w/Butterworth for dry bulk trailer 0. 8. 3. 1. 0. 0. 3. 5. 57 3 0 1 57 57 6 7 Number of Total water trailers use, m 84 321 316 123 0 0 68 78 990 47.6 2,666.0 954.5 ' 139.3 0 0 243.9 441.7 4,493.3 MEK - methyl ethyl ketone; MIBK - methyl isobutyl ketone. 12 ------- TABLE 7. COMMODITY/TANK TRUCK DATA FOR ONE TERMINAL DURING ONE MONTH OF OPERATION (4) Cleaning method number Commodity No. of trailers cleaned Uran fertilizer PAPI—isozylate Ethyl chloride Alum Water for glue Water softener Caustic soda (50%) Silicate soda Acetic acid Phosphoric acid Spent acid Sulfuric acid Hydrochloric acid Corrosive liquid Solvent Toluene Xylene IPA—isopropyl alcohol Sodium MET EDA—ethylene diamine DTA—diethylene triamine Poly amines Vinyl acetate Cyescal Phenol Alcohol Petroleum chemicals Peroxide Biphenyl Sodium bichromate Sodium methylate PA-phthalic anhydride Acetone Adaline Ferric chloride TTA—Amine 220 AN—acrylonitrile Protein feed supplement Calcium chloride Styrene Methyl acrylate 16 2 10 53 2 1 123 2 22 1 47 87 38 1 18 26 2 23 1 15 8 7 23 3 32 22 1 4 2 9 3 6 9 4 3 3 8 2 1 2 1 tcontinued) 13 ------- TABLE 7 (continued). Cleaning method number Commodity No. of trailers cleaned 3 (cont.) Weed killer Shell pan DMK—dimethyl ketone Benzene Pentylamine Ethylene glycol MEK—methyl ethyl ketone ITA Mineral spirits DAA—diacetone acrylonitrile NBA—normal butyl alcohol Methanol Butyl cellosolve Formaldehyde Oxylene Naphtha MIBK—methyl isobutyl ketone Demineralized water Turpentine Oxital—ethylene glycol mono- ethane ether TRI Clean D 4 Glue Paint Resin Water treating compound Coastal pale oil Petroleum oil Cotton oil Script set 7 Diesel oil Petrolatum Ink oil Strip oil Hi Boiler Oil Tall Oil Insulator oil (new) CPTIC—crude petroleum 8 Potash and fertilizers Plastic pellets 4 1 4 1 1 3 14 2 3 4 1 3 1 24 1 1 4 1 2 1 2 72 2 30 5 7 3 2 2 21 16 2 13 2 5 1 8 78 aCleaning method numbers correspond to those tested in Table 6. 14 ------- TABLE 8. PRODUCTION OF STEEL DRUMS9 Size 0.2-m3 (55-gal) 0.2-m3 (55-gal) 0.2-m3 (55-gal) 0.2-m3 (55-gal) 0.11-m3 (30-gal) Drum Gauge 18 18 20/18 20/18 20/18 Production, thousands Type Tight head Open head Tight head Open head Tight head and open head 1972 10,851 3,231 9,359 2,044 2,757 1973 12,032 3,426 9,917 2,234 b 1974 12,357 3,083 12,349 2,484 b 1975 8,352 2,066 8,419 1,956 b Personal communication from the National Barrel and Drum Association, 1976. b Not available. Drums constructed of 18-gauge steel have an average life with total cleaning of eight trips. Drums constructed with 20-gauge bodies and 18-gauge heads have an average life of three trips (private communication; estimated by M. Hershon, National Barrel and Drum Association). Not all drums are cleaned, especially those of thinner construction. If all 0.2-m3 (55-gal) drums were cleaned for their average life, 121 million drums would be cleaned each year. Tight-head drums which have carried materials that are easy to clean are steamed or washed with caustic. Drums used to carry materials which are difficult to clean are burned out either in a furnace or in the open. Tight-head drums have the head cut out before burning and are reconditioned as open-head drums. Steam cleaning is accomplished by inserting a steam nozzle into the drum, with vapors going to the atmosphere and condensed water going either to a sewer or onto the ground. Caustic washing is done by tumbling the drum with a charge of hot caustic solution and some pieces of chain. The caustic solution is recycled until spent and then neutralized and sent to the sewer. Some cleaners pond the spent caustic to allow sludge settling before sending the liquid to the sewer. The sludge is periodically removed from the pond and landfilled. There are few, if any, air emissions from caustic cleaning. Fiber drums are lined with disposable plastic bags. are disposed of in an industrial trash container. Old bags Drum burning furnaces are of two basic types; batch and contin- uous. A batch-type furnace is designed to hold one 0.2-m3 (55-gal) drum at a time. The same chamber is used to process 0.11-m3 (30-gal) drums. Several gas burners are arranged to completely bathe the drum in flame. The contents, lining, and outside paint of the drum are completely burned away within a 15 ------- nominal 4-minute period with the drum reaching a temperature of at least 480°C (5). Continuous-type furnaces accomplish the same combustion process on each drum but are designed with a conveyor to pass a continu- ous stream of drums through a preheat zone, a combustion zone, and a postcombustion zone. The drums are given the same 4-minute combustion period at a temperature of at least 480°C. The tem- perature of the drums must not exceed 540°C since this would cause excessive scale and warping (5). After the combustibles are consumed, the drums are allowed to cool. They are then shot-peened to remove ash and char. Dents are removed, the drums are tested hydraulically, and protective coatings are applied (5). Emissions from the combustion process are vented to an after- burner or secondary combustion chamber where" the gases are raised to at least 760°C for a minimum of 0.5 second. These conditions should ensure complete combustion of elemental carbon and organic combustion contaminants in the primary effluent (5). Open air burning is far less efficient than furnace burning be- cause there is no way to control combustion air and temperatures. Since there is no feasible way of controlling emissions from open burning, incompletely burned combustion products can be released to the atmosphere. The average amount of material removed from each drum is approximately 2 kg (5). GEOGRAPHICAL DISTRIBUTION Rail Tank Cars Information on rail tank car cleaning racks from the Railway Progress Institute (personal communication with A. M. Skogsberg, 16 December 1976) and Railway Age Magazine (6) is shown by state in Table 9. Rail tank cars operated by chemical manufacturing companies to haul their own products or raw materials account for about 10% of car ownership (3). All such cars are in dedicated service and are rarely cleaned. Therefore, the cleaning of tank cars by these companies is estimated to represent less than 5% of the total cleaning nationwide. The cleaning conducted by each of these companies is governed by the waste treatment regulations applicable to its industry. (5) Air Pollution Engineering Manual, Second Edition, J. A. Danielson, ed. Publication No. AP-40, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, , May 1973. 987 pp. (6) Railway Age Directory of Contract Car Repair Facilities. Railway Age, 177(13):44-49, 1976. 16 ------- TABLE 9. RAIL CAR CLEANING BY STATE NO. Of cleaning State racks Alabama Arkansas California Delaware Georgia Illinois Indiana Iowa Kansas Kentucky Louisiana Maryland Mississippi Missouri Montana Nebraska New York North Carolina Ohio Oklahoma Oregon Pennsylvania Tennessee Texas Virginia West Virginia Wyoming TOTALS 2 3 5 1 3 2 2 1 5 2 3 1 1 2 1 2 2 1 1 1 1 5 1 12 1 3 1 65 No. of cars cleaned/yr 500 3,000 2,000 100 2,000 2,000 4,750 100 5,000 200 2,500 500 750 600 500 200 1,000 75 1,750 500 375 1,850 75 5,500 75 1,300 20 37,220 Tank Trucks Interior washing of tank trucks in conducted at tank truck dis- patch terminals, which are distributed throughout the states, but they are heavily concentrated in areas such as Chicago, Northern New Jersey, the Kanawha and Ohio River Valleys, and the Louisi- ana-Texas Gulf Coast area where large chemical manufacturing com- plexes are located (7). There is no adequate data base on how (7) Final Report on Cost of Implementation and Capabilities of Available Technology to Comply with P.L. 92-500; Volume IV: Industry Categories 29-38. Prepared for the National Com- mission on Water Quality by Battelle Columbus Laboratories, Columbus, Ohio, July 3, 1975. 17 ------- many tank truck dispatch terminals actually perform cleaning operations. Many truck fleets are too small to have their own cleaning racks and must .have their cleaning done for them at larger terminals. Even the National Tank Truck Carriers organi- zation does not have data that they consider adequate. Based on a limited study of the transportation segment, Battelle/Columbus has estimated that there are about 500 terminals involved in tank truck cleaning (7). Table 10 shows, by state, the distribution of tank truck cleaning, based on Battelle's estimates and other information obtained from conversations with industry members. Drum Cleaning and Burning The National Barrel and Drum Association (NBADA) is made up of 133 member companies, 35 of whom have burning facilities. NBADA estimates that the membership comprises at least 90% of the total business and approximately 33.3% of the total number of companies involved in the industry (personal communication with Pamela Terry, NBADA, September 24, 1976). Examination of manufacturing indexes and the yellow pages for several cities indicates that the 1/3 to 2/3 ratio holds fairly well for distribution of loca- tions also. Table 11 shows NBADA member drum cleaning facilities by state. From this information, it is estimated that there are 24,680,000 drums cleaned per year with 10,100,000 of these burned clean. The total number of companies in the United States is estimated at 399 with 39 having burning facilities. 18 ------- TABLE 10. TANK TRUCK CLEANING BY STATE (7) NO. Of cleaning State terminals Alabama Arizona Arkansas California Colorado Connecticut Delaware Florida Georgia Idaho Illinois Indiana Iowa Kansas Kentucky Louisiana Maine Maryland Massachusetts Michigan Minnesota Mississippi Missouri Montana Nebraska Nevada New Hampshire New Jersey New Mexico New York North Carolina North Dakota Ohio Oklahoma Oregon Pennsylvania Rhode Island South Carolina South Dakota Tennessee Texas Utah Vermont Virginia 10 3 10 23 5 10 3 5 6 2 30 25 7 19 20 25 1 15 15 15 11 3 10 5 5 1 3 25 2 20 3 2 20 15 2 15 2 5 3 8 30 2 1 15 No. of tank trucks cleaned/yr 81,000 25,000 90,000 240,000 55,000 82,000 35,000 50,000 45,000 20,000 290,000 220,000 70,000 172,000 195,000 250,000 6,500 110,000 150,000 160,000 120,000 30,000 125,000 45,000 40,000 6,900 15,000 300,000 19,000 190,000 35,000 19,000 200,000 150,000 21,000 155,000 10,000 50,000 29,000 90,000 400,000 20,000 8,800 125,000 (continued) 19 ------- TABLE 10 (continued) State Washington West Virginia Wisconsin Wyoming TOTALS No- of cleaning terminals 10 18 10 5 500 No. of tank trucks cleaned/yr 91,000 200,000 121,000 48,000 5,010,000 TABLE 11. NBADA MEMBER DRUM CLEANING AND BURNING BY STATE No. of cleaning State facilities Alabama California Colorado Connecticut Florida Georgia Illinois Indiana Iowa Kansas Kentucky Louisiana Maryland Massachusetts Michigan Minnesota Missouri Nebraska New Hampshire New Jersey New York North Carolina Ohio Oklahoma Oregon Pennsylvania Rhode Island South Carolina Tennessee Texas Virginia Washington Wisconsin Wyoming TOTAL NBADA members TOTAL estimate, of all drum cleaners 1 14 3 2 3 4 7 2 1 1 2 2 4 2 5 4 2 1 1 10 10 4 15 1 1 12 1 2 2 3 3 2 5 1 133 399 No. of burning facilities 0 5 0 0 0 2 2 0 0 0 2 0 1 1 3 3 0 0 0 2 2 1 2 0 0 3 1 1 0 1 0 1 2 0 35 39 10 3 Drums washed 84 1,454 251 168 240 450 708 168 83 85 280 180 392 225 580 508 169 85 80 920 890 380 1,390 100 80 1,160 140 225 150 328 240 224 531 85 13,123 14,580 10 3 Drums burned 0 1,300 0 0 0 500 530 0 0 0 525 0 265 250 785 750 0 0 0 525 500 260 700 0 0 720 230 250 0 300 0 220 480 0 9,090 10,100 20 ------- SECTION 4 EMISSIONS SELECTED POLLUTANTS AND EMISSIONS The great diversity of commodities (>700 chemicals) carried by rail tank cars, tank trucks, and drums makes it nearly impossi- ble to sample and obtain emission factors for every possible material. In the drum cleaning and burning industry, only com- posite estimates are possible for a wide mixture of materials. Sampling of emissions from the cleaning of representative indi- viual commodities is practical with tank cars and tank trucks. In order to achieve a practical, but representative, picture of these emissions, the organic chemicals hauled by the carriers were broken down into classes characterized by high, medium, and low viscosities and by high, medium, and low vapor pressures. Viscosity affects the quantity of material remaining in the tank; low viscosity materials drain readily while high viscosity mate- rials do not. Vapor pressure affects the air emissions since high vapor-pressure materials volatilize more readily during cleaning and tend to lead to higher emission rates. After the classes of chemicals had been established, the selec- tion of the particular chemical to be sampled for was dictated by the specific materials which were being cleaned during the sam- pling visits. Table 12 presents the chemicals sampled, the total of each per truck or car, and the TLV® (8, 9) (threshold limit value) of each. Virtually all of the air and water pollutants are removed from the tank during the first washing cycle. This takes 45 minutes to 1 hour for tank trucks and 1 hour to 2 hours for rail tank cars. Subsequent rinsing adds only small (<2% est.) quantities of washing solution to the wastewaters. (8) TLVs® Threshold Limit Values for Chemical Substances and Physical Agents in the Workroom Environment with Intended Changes for 1975. American Conference of Governmental Indus- trial Hygienists, Cincinnati, Ohio, 1975. 97 pp. (9) Sax, N. I. Dangerous Properties of Industrial Materials, Third Edition. Reinhold Book Corporation, New York, New York, 1968. 1251 pp. 21 ------- TABLE 12. MEASURED EMISSIONS FROM TANK CAR AND TANK TRUCK CLEANING Compound Chemical class Vapor pressure Viscosity Measured emission Total concen- emissions, tration, mg/m3 mg/m3 Ref. TLV Acetone Perchloroethylene Methyl methacrylate Phenol Propylene glycol Ethylene glycol Chlorobenzene O-Dichlorobenzene Creosote High High Medium Low Low Low Medium Low Low Low Low Medium Low High High Medium Medium High 311/truck 2 15/ truck 32. 4/ truck 5 . 5/truck 1 . 07/truck <0.32/car 15.7/car 75.4/car 2,350/car (8-hr) 654 526 79.1 14.0 4.3 <0.2 8.8 94.3 118 2,400 670 410 19 260 260 350 300 22 8 8 8 8 _b 8 8 8 9 Total emissions = (emission rate) x (emission volume). No TLV listed; assumed to be same as that for ethylene glycol based on comments in Sax (9). Wastewater is subject to great variability and, even with a good treatment system, is difficult to treat to consistently accepta- ble levels. Table 13 presents waste treatment plant effluent data (API separator, pH adjustment, aeration basin, sedimenta- tion) for one month of operation supplied by one tank truck terminal official (4). This terminal is adding more treatment process (equalization, air flotation, filtration, biological) to improve their treatment capability. Another tank truck terminal official reports the treatment plant influent and effluent data shown in Table 14 which represent the results of tests taken over a 6-month operating period (10). This treatment facility (Figure 1) (10) is a 45-m3/day (12,000- gal/day) demonstration plant funded by the U.S. Environmental Protection Agency. Reported wastewater treatment data for several rail tank car cleaning stations are shown in Table 4 in Section 3 (3). Samples taken from the stack of a drum burning furnace were analyzed for unburned organic materials and for organic prod- ucts from incomplete combustion. Analysis showed no detectable levels (<5 x 10~6 g/m3) of organic materials. This indicates (10) O'Brien, J. E. A Demonstration Plant for the Treatment of Waste Waters from Tank Truck Cleanings. Presented at the American Institute of Chemical Engineers National Meeting, Atlantic City, New Jersey, September 1, 1976. 8 pp. 22 ------- TABLE 13. WASTE TREATMENT PLANT EFFLUENT DATA, JUNE 1973 (4) Total residue , TSS , Date 6/1 6/4 6/5—2.9" rain 6/6 6/7 6/8 6/11 6/12 6/13 6/14 6/15 6/18 6/19 6/20 6/21 6/22 6/25 6/26 6/27 6/28 Monthly average pH mg/ 7.72 1,315 6.73 1,199 6.94 1,196 7.45 1,469 7.47 499 7.12 548 8.08 755 7.62 677 8.06 448 8.90 409 7.68 686 8.23 573 8.11 692 7.92 815 7.95 880 7.51 4,602 8.12 2,788 8.02 2,402 8.36 2,060 8.24 1,744 7.81 1,288 fc rng/g, 478 442 342 1,168 175 242 49.2 584 131 85.6 262 24 32.6 131 247 61.2 94 22 73.2 76 186 VSS , BOD , COD, mg/& mg/£ mg/fc 120 1 148 122 238 36 42 14.8 90 20 16.4 49 12.8 12.4 33 44 21.2 29 26.8 26.8 20.8 56 ,364 460 475 61 185 40 11.4 8.3 10.1 13.3 24 13.2 28 63 73 25 17.8 3,274 1,431 1,373 269 268 110 66 64 30 42 94 69 144 215 254 251 183 169 235 139 434 Settleable Temperature , sol ids , °C V«^— ^^^^^V~^M^^^ta^M«^^^H**^H« 25 21 27 .5 30 .8 23 .1 .2 24 .5 28 .3 28 28 28 26 25 25 23 31 26 26 mg/fc 96 30 24 . 548 9 12 0.4 70 10 15.6 12 9.2 12.4 112 13.6 8.4 5.6 4.4 11.2 53 TSS = total suspended solids, COD = chemical NOTE: Some of oxygen demand. the quantities VSS = volatile in Table 13 are suspended shown per solids liter , BOD = biochemical (&) , which is the s\ oxygen demand, rstem of units used in Reference 4. These values can be converted to the SI metric system using the equality, 1 I = 0.001 m3. Blanks indicate data not reported. ------- TABLE 14. TREATMENT PLANT OPERATING RESULTS— MATLACK, INC., SWEDESBORO, N.J. (10) Parameter PH Color units Turbidity, FTU COD, g/m3 BOD5 , g/m3 Oil and grease, g/m Phenols, g/m3 Suspended solids, g/m3 Raw feed 10.5 to Over Over 1,800 600 110 1 300 to to to to to 12.5 500 500 11,000 2,000 350 250 1,300 Effluent 6.5 10 125 20 0 to to _D to to to 0,1 _b 8.5 50 300 100 1 Formazin turbidity units; a standard unit of turbidity based upon a known chemical reaction. 'Data not reported. RAW WASTE SURFACE SKIMOIL I (RESALE) FLOTATION /•CELL pH PRESSURE / ' CELL ACTIVATED CARBON TRANSFER TANK SPENT CARBON DISCHARGE RECYCLE Figure 1. Wastewater treatment system, Matlack, Inc., Swedesboro, New Jersey (10). 24 ------- that a properly operated furnace is capable of essentially total destruction of waste organic materials encountered in drum burning. The drum cleaning companies visited had closed drum washing sys- tems with no discharge of wastewaters. It is reasonable to assume that wastewaters from drum washing would present the same treatment problems as those from tank truck and rail tank car cleaning and would be treatable by use of the same basic treat- ment technology. DEFINITIONS OF REPRESENTATIVE SOURCES Four representative sources are defined for use in determining the source severity for each type of cleaning; i.e., rail tank car, tank truck, drum burning and washing, and drum washing only. Due to the lack of adequate published data, these definitions are based on estimates made by several officials of companies in the industry and by the industrial organizations (Railway Progress Institute, and National Barrel and Drum Association). Representative Rail Tank Car Cleaning The representative rail tank car cleaner cleans 575 cars/yr (5.5 cars/day). The commodities hauled and cleaned are 35% pe- troleum products (excluding gasoline, fuel oils, and lubricating oils.), 20% organic chemicals, 25% inorganic chemicals, 15% com- pressed gases, and 5% food products. The emission height (height of car) is 4 m. Representative Tank Truck Cleaner The representative tank truck cleaner cleans 10,000 tank truck trailers per year. This is equivalent to 20,000 nondedicated tank trucks cleaned 5 times per week, 50 weeks per year at the 500 cleaning sites (Section 3.). The commodities hauled and cleaned are 15% petroleum products (excluding gasoline, fuel oils and lubricating oils), 35% organic chemicals, 35% inorganic chemicals, 5% food products, and 10% others (paints, inks, naval stores, plastic pellets, etc.) The emission height ("height of truck is 3.55 m. Representative Drum Cleaners Drum Cleaner with Burning Equipment (Type a)— The representative drum cleaner with burning equipment cleans approximately 400,000 drums/yr (assuming 260 days/yr, 1,540 drums/day), of which 65% are burned and 35% are washed. Emis- sion heights are 10 m for burning and 1 m for washing. Drum Cleaner with Washing Only (Type b)— The representative drum cleaner, with washing only, cleans 83,800 drums per year. Emission height (top of drum) is 1 m. 25 ------- Both categories of drum cleaners clean drums used to carry a vast variety of commodities, with organic chemicals (including sol- vents) accounting for 50%. The remaining 50% includes inorganic chemicals, asphaltic materials, elastomeric materials, printing inks, paints, food additives, fuel oils, etc. ENVIRONMENTAL EFFECTS OF AIR EMISSIONS Maximum Ground Level Concentrations The maximum ground level concentration, Xmax, of each pollutant resulting from rail tank car and tank truck cleaning and from drum burning and washing was estimated by Gaussian plume disper- sion meteorology. ^max values for each type of cleaning are shown in Table 15. For comparison, the TLV's and ambient air quality standards (AAQS) are also listed. Air emissions from drum washing are negligible since each drum is washed by charging with cleaning solution, putting in some chain, closing the drum, and tumbling it. During this cycle, no vapors can escape except during charging and dumping. Emission rates would therefore be less than in rail car and tank truck cleaning, and these are shown in Table 15 to be extremely low. Sampling and analysis for organic materials in the stack gases from drum furnaces show no detectable organics present (detec- tion limit 5 x 10~6 g/m3). The primary combustion chamber operates at less than 530°C with 200% excess air. Secondary com- bustion is accomplished at approximately 700°C with 100% excess air. These conditions are conducive to complete combustion of the organic materials in the drums, but the temperatures are low enough to prevent the formation of large quantities of nitrogen oxides (NOX) . Also, the concentrations of carbon monoxide (CO) and particulates would be small. Automobile body incinerators operate at conditions analagous to drum furnace conditions but with less excess air. Using emission factors for particulates and N02 from auto body incinerators (11) , the emission factors from drum burning are estimated (see Appendix A) . Maximum ground level concentrations are not given for organics, carbon monoxide, or hydrocarbons since the stack concentrations are below detection. The following equation was used for the calculation of X (12) : X = 2 Q (1) max 7TH2eu (11) Compilation of Air Pollutant Emission Factors, Second Edi- tion. Publication No. AP-42, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, April 1973. p. 2.2.-1. 26 ------- where Q = mass emission rate, g/s u = U.S. average wind speed, 4.47 m/s H = emission height, m e = 2.72 TT = 3.14 Environmental Effects To obtain an indication of the hazard potential of the emission source, the source severity, S, is defined as (12): _ xmax b ~ F where ^max is the time-averaged maximum ground level concentra- tion of each pollutant emitted from a representative source of tank or for criteria pollutants and "a corrected" threshold limit value (TLV • 8/24 • 1/100) for noncriteria pollutants. The source severity represents the ratio of time-averaged maxi- mum ground level exposure to the hazard level of exposure for a particular pollutant. x"max is the maximum ground level concentration (Xmax) averaged over a given period of time. The averaging time is 24 hours for noncriteria pollutants. For criteria pollutants, averaging times are the same as those used in the primary ambient air quality standards. For the tank truck and rail tank car cleaning operations, the time periods during which emissions occur are approximately 1 hr for tank trucks and 2 hr for rail tank cars. These times cor- respond to the initial wash cycle of each carrier. Since it is rare for more than one truck or car containing a particular material to be cleaned in any one day, time-averaging of Xmax for that particular pollutant over a 24-hr period would result in an extremely low Xmax and S. Using Xmax in place of Xmax in Eclua~ tion 1 gives a worst case source severity which represents the maximum hazard level of exposure for a particular pollutant at any time during a normal 24-hr period. The values for Xmax and s for each pollutant from each type of cleaning are given in Table 15. The worst case source severity factors for the pollutants from tank truck cleaning are <0.1 for (12) Serth, R. W., and T. W. Hughes. Source Assessment: Phthalic Anhydride (Air Emissions). EPA-600/2-76-032d, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, December 1976. 154 pp. 27 ------- most classes of materials and just over 0.1 for the high vapor- pressure, low viscosity class. For rail tank car cleaning, the worst case source severity factors are <0.1 with the materials* sampled except for one creosote car which was exceptionally dirty. TABLE 15. MAXIMUM GROUND LEVEL CONCENTRATIONS AND SEVERITY FACTORS FOR DIFFERENT EMISSIONS Type of cleaning Tank truck Rail tank car Drum burning Emission Acetone Perchloroethylene Methyl methacrylate Phenol Propylene glycol Ethylene glycol Chlorobenzene o-Dichlorobenzene Creosote Particulates NO X yS/$ 359 248 37 6.35 1.24 <0.14 7.14 34.3 267 73 1.2 TLV, g/m3 2.4 0.67 0.41 0.019 0.26 0.26 0.35 0.3 0.022 _b _ AAQS, (13) g/m3 a ~a ~a ~a a a ~a a 0.00026° 0.0001" Source severity 0.045 0.11 0.027 0.100 0.0014 0.00017 0.0061 0.034 3.6 0.28 0.012 AAQS not defined for these materials. Not applicable. 24-hr average. d Annual average. For drum burning, the source severity factors are very low with particulates accounting for the highest severity of 0-56. Sever- ity distributions for air emissions are not presented since esti- mates were used to define the representative source. A survey of the industry would be required to define ranges or limits on source size and this would necessitate an extensive effort. Contribution to Total Air Emissions i The total air emissions from a particular source for each state and the nation are determined by multiplying the emission factor (13) Code of Federal Regulations, Title 42 - Public Health, Chapter IV - Environmental Protection Agency, Part 410 - National Primary and Secondary Ambient Air Quality Standards, April 28, 1971. 16 pp. 28 ------- of a pollutant by the source production. For tank truck and rail tank?car cleaning, since the exact distribution of the represen- tative chemical classes in total cleaning is unavailable, the emission factor for acetone (the highest measured) was used to calculate state and national burdens for tank truck cleaning; the emission factor for creosote was used for rail tank car cleaning. The total organic emissions from tank truck and rail tank car cleaning in each state were compared with the reported total hydrocarbon emission burden for that state (14), and these are shown in Table 16. Tank truck and rail tank car cleaning contri- bute <0.02% to the organic pollutant burden of the states or nation. Total hydrocarbon emissions from drum washing or burning are negligible. Total particulate emissions from drum burning contribute <0.023% of any state emission burden and 0.0007% of national emissions burden (Table 17). Affected Population To obtain a quantitative evaluation of the population influenced by a concentration of emissions from a source, the area exposed to the time-averaged ground level concentration, x", for which X/Fi^l.O is obtained by determining the area within the isopleth for x" (15) , and the number of people within the exposed area is then calculated by using a proper population density. As shown in Table 15, the source severities (except for creosote) from rail tank car and tank truck cleaning, and from drum wash- ing and burning are below 1.0, even though these are worst case calculations. When no area is exposed to a severity £1.0, the affected population for these operations is zero. The creosote emission was from an exceptionally dirty car and is not consid- ered to be typical of the industry. ENVIRONMENTAL EFFECTS OF WATER POLLUTANTS Effluent Concentration The effluent concentrations, CD, are defined as the total mass of suspended or dissolved material in a unit volume of effluent at (14) Eimutis, E. C., and R. P. Quill. Source Assessment: State- by-State Listing of Criteria Pollutant Emissions. EPA-600/ 2-77-107b, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, July 1977. 146 pp. (15) Turner, D. B. Workbook of Atmospheric Dispersion Estimates Public Health Service Publication No. 999-AP-26, U.S. Department of Health, Education, and Welfare, Cincinnati, Ohio, 1969. 64 pp. 29 ------- TABLE 16. MASS OF EMISSIONS FROM TANK TRUCK AND RAIL TANK CAR CLEANING AND COMPARISON WITH STATE AND NATIONAL HYDROCARBON EMISSION BURDENS u> o Carriers hauling organics, no. cleaned State Alabama Arizona Arkansas California Colorado Connecticut Delaware Florida Georgia Idaho Illinois Indiana Iowa Kansas Kentucky Louisiana Maine Maryland Massachusetts Michigan Minnesota Mississippi Missouri Montana Nebraska Nevada Trucks 28,350 8,750 31,500 84,000 19,250 28,700 12,250 17,500 15,750 7,000 101,500 77,000 24,500 60,200 68,250 87,500 2,275 38,500 52,500 56,000 42,000 10,500 43,750 15,750 14,000 2,415 Rail cars 100 0 600 400 0 0 20 0 400 0 400 950 20 1,000 40 500 0 100 0 0 0 150 120 100 40 0 Total emissions, metric tons/yr Trucks 8.82 2.72 9.80 26.12 6.00 8.93 3.81 5.44 4.90 2.18 31.57 23.95 7.62 18.72 21.23 27.21 0.71 11.97 16.33 17.42 13.06 3.27 13.61 4.90 4.35 0.75 Rail cars 0.24 0 1.41 0.94 0 0 0.05 0 0.94 0 0.94 2.23 0.05 2.35 0.09 1.18 0 0.24 0 0 0 0.35 0.28 0.24 0.09 0 Percent of state (14) hydrocarbon burden Trucks 0.0014 0.0014 0.0050 0.0012 0.0031 0.0041 0.0060 0.0009 0.0011 0.0026 0.0017 0.0040 0.0024 0.0060 0.0065 0.0014 0.0006 0.0040 0.0037 0.0024 0.0032 0.0017 0.0033 0.0018 0.0034 0.0014 Rail cars 0.00004 0 0.00072 0.00004 0 0 0.00008 0 0.00021 0 0.00005 0.00037 0.00002 0.00076 0.00003 0.00006 0 0.00008 0 0 0 0.00018 0.00007 0.00009 0.00007 0 (continued) ------- TABLE 16 (continued) !— Carriers hauling organics, no. cleaned State New Hampshire New Jersey New Mexico New York North Carolina North Dakota Ohio Oklahoma Oregon Pennsylvania Rhode Island South Carolina South Dakota Tennessee Texas Utah Vermont Virginia Washington West Virginia Wisconsin Wyoming Trucks 5,250 105,000 6,650 66,500 12,250 6,650 70,000 52,500 7,350 54,250 3,500 17,500 10,150 31,500 140,000 7,000 3,080 43,750 31,850 70,000 42,350 16,800 Rail cars 0 0 0 200 25 0 0 100 55 720 0 0 0 25 1,100 0 0 25 0 220 0 4 Total emissions, metric tons/yr Trucks 1.63 32.66 2.07 20.68 3.81 2.07 21.77 16.33 2.29 16.87 1.09 5.44 3.16 9.80 43.54 2.18 0.96 13.61 9.91 21.77 13.17 5.22 Rail cars 0 0 0 0.47 0.06 0 0 0.24 0.13 1.69 0 0 0 0.06 2.59 0 0 0.06 0 0.52 0 0.01 Percent of state (14) hydrocarbon burden Trucks 0.0018 0.0040 0.0014 0.0016 0.0009 0.0029 0.0019 0.0048 0.0010 0.0019 0.0017 0.0006 0.0035 0.0027 0.0020 0.0022 0.0023 0.0037 0.0029 0.0187 0.0025 0.0094 Rail cars 0 0 0 0.0004 0.0001 0 0 0.00007 0.00006 0.00019 0 0 0 0.00002 0.00012 0 0 0.00002 0 0.00045 0 0.00002 NATIONAL 1,730,000 7,440 538.05 87.47 0.0022 0.00037 ------- TABLE 17. MASS OF EMISSIONS FROM DRUM BURNING AND COMPARISONS WITH STATE AND NATIONAL PARTICULATE EMISSION BURDENS State No. Of barrels burned Total emissions, metric ton/yr TOTAL 10,100,000 119.6 Percent of state particulate burden California Georgia Illinois Kentucky Maryland Massachusetts Michigan Minnesota New Jersey New York North Carolina Ohio Pennsylvania Rhode Island South Carolina Texas Washington Wisconsin 1,400,000 550,000 590,000 580,000 290,000 280,000 870,000 830,000 580,000 550,000 290,000 780,000 800,000 260,000 280,000 330,000 240,000 530,000 16.8 6.6 7.0 7.0 3.5 3.3 10.3 9.9 7.0 6.6 3.5 9.2 9.5 3.0 3.3 4.0 2.9 6.4 0-0017 0.0017 0.0007 0.0013 0.0007 0.0034 0.0014 0.0037 0.0046 0.0041 0.0007 0.0006 0.0005 0.023 0.0017 0.0008 0.0018 0.0015 0.0007 a given temperature and pressure. In the raw effluent from representative cleaning operations, Cp was estimated on the basis of available information. Concentrations for rail tank car cleaning were taken as the average of the values shown for the first site in Table 4. This site, except for cleaning more cars, closely approximate the representative source. For tank truck cleaning, the raw effluent averages shown in Table 14 were used since this terminal's cleaning operation is similar to the representative source (30 trucks/day versus 40/day for the rep- resentative plant). No effluent concentration data were avail- able for drum washing operations. The assumption was made, therefore, that the total material cleaned from drums was dis- tributed in the same percentage ratios as the effluents from tank trucks with no allowance made for removal of settleable solids (see Appendix A). The C^ values for all of these repre- sentative cleaning operations along with effluent flow rates are shown in Table 18. Source Severity Determination of the source severity for the representative sources gives a measure of the effluent species concentration 32 ------- relative to a potentially hazardous or permissible concentration. The source severity (defined in Appendix B) is calculated as follows (16): (3) where C = exposure level concentration, g/m33 F = hazard factor (Table 18) VD = volumetric flow rate of discharge, m3/s VR = volumetric flow rate of receiving waters, m3/s (national average river flow rate = 856 m3/s) Cj-j — concentration in raw effluent, g/m3 Severity values were calculated using Equation 3 for oil and grease, phenol, and suspended solids for each of the representa- tive sources, and these are shown in Table 19. The severity of the total oxygen demand potential (STOD) °f a discharge is the ratio of the potential total oxygen deficit divided by a permis- sible total oxygen deficit. Thus, Equation 3 was modified as follows to permit calculation of the severity of the total oxygen demand of a discharge (17): V ~ (TOD) q = R (A\ S(TOD) - Cs - (DO)WQC where TOD = total effluent oxygen demand, g/m3 C,.. = saturated dissolved oxygen concentration at b 10°C (= 11.3 g/m3) (DO) , = dissolved oxygen fresh water quality criteria (=5.0 g/m3) a g/m3 is equivalent to mg/£, which is the normal nonmetric unit used for concentration. (16) Decision Criteria for Water Discharges. Draft prepared for EPA review under Contract 68-02-1874 by Monsanto Research Corporation, Dayton, Ohio, 1976. 4 pp. (17) Eimutis, E. C., T. J. Hoogheem, and T. W. Hughes. Briefing Document: Water Source Severity and Initial Water Prioriti- zation Structures. Draft prepared under EPA Contract 68-02-1874 by Monsanto Research Corporation, Dayton, Ohio, September 21, 1976. 12 pp. 33 ------- TABLE 18. EFFLUENT CONCENTRATIONS (CD) AND HAZARD FACTORS (F) FOR REPRESENTATIVE SOURCES Effluent concentrations, g/m3 Source Rail tank cars Tank trucks Drums, type a Drums, type b Hazard factor, F Oil and grease 2,005 230 148 148 0.01 (18) . COD 20,100 6,400 4,130 4,130 fa 6.3 Phenol 75 130 84 89 0.001 (18) Suspended solids 10,025 800 517 517 25 (18) Flow, m3/day 61 45 25 15 a EPA fresh water criteria or equivalent. [C - (DO) ] factor in Equation 4, allowable dissolved oxygen depletion. y TABLE 19. SOURCE SEVERITIES FOR REPRESENTATIVE SOURCES Source severity Oil and Suspended Source type grease TOD solids Phenol Rail tank car 0.16 0.0034 0.00033 0.062 Tank truck 0.014 0.00081 0.000020 0.080 Drums, type a,b 0.0030 0.00017 0.000004 0.017 The representative sources have been defined in Section 4. Since TOD values are not available, Equation 4 was modified to (17): y?- 1.3 (COD) • STOD = [Cs - (DO)WQ(J ( where COD = chemical oxygen demand, g/m3 Severity values for TOD are shown in Table 19 for each of the representative sources. In all of the source severity deter- minations, the assumption was made that the raw effluent was (18) Quality Criteria for Water. EPA-440/9-76-023, U.S. Environ- mental Protection Agency, Washington, D.C. 501 pp. 34 ------- discharged with no treatment, thus giving a worst case determi- nation. In practice, oil and grease separation and batch treat- ment of phenol provide a lower actual impact than the calcula- tions indicate. Reductions in oxygen demand and suspended solids are also accomplished in the treatment processes used by the different cleaning facilities so these impacts are in practice, lower than the calculations indicate. Severities are low in all cases with the highest value being 0.16. Severity distributions for effluent species are not presented since estimates were used to define the representative source. A survey of the industry would be required to define ranges or limits on source size and this would necessitate an extensive effort. Contribution to State and National Burdens The total discharge quantities of oil and grease, COD, phenol, and suspended solids, assuming no treatment, were calculated by dividing the production of the representative source into state production totals and multiplying this by the discharge per representative source. These quantities are shown, by state and nation, for each type of cleaning operation in Tables 20, 21, and 2 2. TABLE 20. RAIL TANK CAR CLEANING CONTRIBUTIONS TO STATE EMISSION BURDENS State Alabama Arkansas California Delaware Georgia Illinois Indiana Iowa Kansas Kentucky Louisiana Maryland Mississippi Missouri Montana Nebraska New York North Carolina Ohio Oklahoma Oregon Pennsylvania Tennessee Texas Virginia West Virginia Wyoming Cars/yr 500 3,000 2,000 100 2,000 2,000 4,750 100 5,000 200 2,500 500 750 600 500 200 1,000 75 1,750 500 375 1,850 75 5,500 75 1,300 20 Oil and grease, metric tons/yr 11 67 44 2.2 44 44 106 2.2 110 4.4 56 11 17 13 11 4.4 22 1.7 39 11 8.3 41 1.7 120 1.7 29 0.4 COD, metric tons/yr 110 670 440 22 440 440 1,100 22 1,100 44 550 110 170 130 110 44 220 17 389 110 83 410 17 1,200 17 290 4.4 Suspended solids, metric tons/yr 56 330 220 11 220 220 530 11 560 22 280 56 83 67 56 22 110 18.3 194 56 42 206 8.3 610 8.3 140 2.2 Phenol, metric tons/yr 0.42 2.5 1.7 0.083 1.7 1.7 3.9 0.083 4.2 0.17 2.1 0.42 0.62 0.50 0.42 0.17 0.83 0.062 1.5 0.42 0.31 1.5 0.062 4.6 0.062 1.1 0.017 TOTALS 37,220 830 8,300 4,100 31 35 ------- TABLE 21. TANK TRUCK CLEANING CONTRIBUTIONS TO STATE EMISSION BURDENS State Alabama Arizona Arkansas California Colorado Connecticut Delaware Florida Georgia Idaho Illinois Indiana Iowa Kansas Kentucky Louisiana Maine Maryland Massachusetts Michigan Minnesota Mississippi Missouri Montana Nebraska Nevada New Hampshire New Jersey New Mexico New York North Carolina North Dakota Ohio Oklahoma Oregon Pennsylvania Rhode Island South Carolina South Dakota Tennessee Texas Utah Vermont Virginia Washington West Virginia Wisconsin Wyoming TOTALS Cars/yr 81,000 25,000 90,000 240,000 55,000 82,000 35,000 50,000 45,000 20,000 290,000 220,000 70,000 172,000 195,000 250,000 6,500 110,000 150,000 160,000 120,000 30,000 125,000 45,000 40,000 6,900 15,000 300,000 19,000 190,000 35,000 19,000 200,000 150,000 21,000 155,000 10,000 50,000 29,000 90,000 400,000 20,000 8,800 125,000 91,000 200,000 121,000 48,000 5,010,000 Oil and grease, metric tons/yr 28 8.7 31 84 19 29 12 17 16 7 101 77 24 60 68 87 2.3 38 52 56 42 10 44 16 14 2.4 5.2 104 6.6 66 12 6.6 70 52 7.3 54 3.5 17 10 31 139 7 3.1 44 32 70 42 17 1,745 COD metric tons/yr 785 242 872 2,326 533 794 339 484 436 194 2,810 2,131 678 1,667 1,890 2,422 63 1,066 1,453 1,550 1,163 291 1,211 436 388 67 145 2,907 184 1,841 339 184 1,938 1,453 204 1,502 97 484 281 872 3,876 194 85 1,211 882 1,938 1,172 465 48,545 Suspended solids, metric tons/yr 98 30 109 291 67 99 42 61 54 24 351 266 85 208 236 303 7.9 133 182 194 145 36 151 54 48 8.4 18 363 23 230 42 23 242 182 25 188 12 61 35 109 484 24 11 151 110 - 242 147 58 6,068 Phenol , metric tons/yr 16 4.9 18 47 11 16 6.9 9.8 8.9 3.9 57 43 14 34 38 49 1.3 22 30 '32 24 5.9 25 8.9 7.9 1.4 3 59 3.7 37 6.9 3.7 39 30 4 30 2 9.6 5.7 18 79 3.9 1.7 25 18 39 24 9.4 986 36 ------- TABLE 22. DRUM WASHING CONTRIBUTION TO STATE EMISSION BURDENS 1 State Alabama California Colorado Connecticut Florida Georgia Illinois Indiana Iowa Kansas Kentucky Louisiana Maryland Massachusetts Michigan Minnesota Missouri Nebraska New Hampshire New Jersey New York North Carolina Ohio Oklahoma Oregon Pennsylvania Rhode Island South Carolina Tennessee Texas Virginia Washington Wisconsin Wyoming TOTALS 103 Drums/yr 93 1,616 279 187 267 500 787 187 92 94 311 200 436 250 644 564 188 94 89 1,022 989 422 1,544 111 89 1,289 156 250 167 361 267 249 590 94 14,580 Oil and grease , metric tons/yr 0.65 11.2 1.9 1.3 1.9 3.5 5.5 1.3 0.64 0.65 2.2 1.4 3.0 1.7 4.5 3.9 1.3 0.65 0.62 7.1 6.9 2.9 10.8 0.77 0.62 8.97 1.1 1.7 1.2 2.5 1.9 1.7 4.1 0.65 101 Suspended solids, metric tons/yr 2.2 39.1 6.8 4.5 6.5 12 19 4.5 2.2 2.3 7.5 4.8 10 6.0 16 14 4.6 2.3 2.2 24.8 24 10 37.4 2.7 2.2 31.2 3.8 6.1 4.0 8.7 6.5 6.0 14 2.3 353 COD, metric tons/yr 18 313 54 36 52 97 152 36 18 18 60 39 84 48 125 109 36 18 17 198 192 82 299 21 17 250 30 48 32 70 52 48 114 18 2,824 Phenol , metric tons/yr 0.37 6.36 1.1 0.74 1.0 2.0 3.1 0.74 0.36 0.37 1.2 0.79 1.7 0.98 2.5 2.2 0.74 0.37 0.35 4.02 3.9 1.7 6.08 0.44 0.35 5.07 0.61 0.98 0.66 1.4 1.1 0.98 2.3 0.37 57 37 ------- SECTION 5 CONTROL TECHNOLOGY PRESENT TECHNOLOGY Practical and economically feasible control of air emissions from the cleaning of rail tank cars and tank trucks does not exist at present except for combustible gases and for water-soluble vapors such as ammonia and chlorine. Tanks carrying combustible gases are filled completely. The displaced gases from the tank are sent to a flare and burned. Vapors of materials such as ammonia and chlorine are absorbed in water and sent to the wastewater stream. Air emissions from drum burning furnaces are controlled by proper operation of the afterburner or secondary combustion chamber of the furnace. There is no feasible control for emissions from open burning of drums. Solution washing of drums yields no air emissions since the drum is closed during the wash cycle. There is currently no control used for emissions from steaming of drums. Most of the material from the drums is carried off with the condensate water, and the air emission is dissipated to the atmosphere. Until the late 1960's little attention was given to wastewater treatment in the rail tank car, tank truck, and drum reclaiming industries. This inattention resulted because the wastewaters were generally low in volume, installations were small, and en- vironmental impacts were considered relatively small in compari- son to those of other industrial pollution sources. Wastewater from an estimated two-thirds of the installations was directed to municipal treatment systems. The rest were discharged directly to surface water streams with only some oil separation. In recent years, both the rail and truck industries have been making a serious effort to improve their wastewater treatment capabilities. No installation is known to have a completely satisfactory treatment system. State-of-the-art treatment tech- nology applicable to rail and truck wastewaters is, for the most part, well known and has been used by manufacturing industries for several years. Wide diversity in the materials entering the wastewaters prevents the use of a single specific treatment sys- tem by all companies. For this reason, tank car and tank truck cleaning companies are approaching their individual problems by 38 ------- using one or more combinations of the methods described below in a building block approach to develop alternate treatment schemes. Gravity Separation Free oil enters the wastewaters from tank contents, exterior washing of tanks, and from leaks or spills. This is removed by gravity separation and incinerated or given to a contracting waste scavenger. The American Petroleum Institute (API) separa- tor design is the most widely used. This separator is a long, rectangular basin which provides enough retention time for the oil to float to the surface for removal. API separators are divided into bays to maintain laminar flow and prevent short circuiting. They are equipped with skimmers that move the oil to the downstream end where it is collected in a slotted pipe or drum. When returning to the upstream end, the skimmers travel along the bottom and move settled solids into a collection trough. The sludge is dewatered and then incinerated or disposed of in a landfill, with the water going to the next treatment step. There are several other designs of gravity separators but the differences only amount to different geometries. Gravity separation is only effective for nonemulsified free oil; emulsified oil is not removed. Other factors affecting the effi- ciency of gravity separation are temperature, oil density, and suspended solids content. Oil removal also takes out some phenols, BOD, and COD since some organics are miscible with oil. Equalization For ease of operation and for a more constant quality of waste- water, the flow and waste concentration to mixed chemical treat- ment systems should be as uniform as possible. Large fluctuation should be dampened in equalization facilities. Equalization is provided in holding tanks or ponds with a reten- tion capacity of 1 day or longer. Baffles and mixers are used to improve equalization. Holding ponds are sometimes used to pro- vide final treatment, relying on long retention times (several days) for settling and biological oxidation. Removal efficien- cies vary widely: 5% to 40% for BOD5, 5% to 30% for COD, 20% to 90% for oil, 10% to 80% for suspended solids, 0% to 70% for phenol, and 30% to 70% for odor (19). Wastewater is directed from the holding basin to an emulsion- breaking and dissolved air-flotation chamber to remove emulsified oils and suspended solids. (19) Manual on Disposal of Refinery Wastes. American Petroleum Institute, Washington, D.C., 1969. 39 ------- Emulsion Breaking This operation can employ either chemical or physical methods. Physical methods include electrolysis, coalescence, filtration, centrifugation, distillation, and temperature change. Chemical methods, aimed at breaking down the stabilizing agent in the emulsion, are more satisfactory. The most practical method of chemically breaking emulsions involves the addition of an acid or acid salt such as sulfuric acid, alum, ferrous sulfate, or ferric chloride. Soda ash may then be used to neutralize the separated water. The resulting free oil and alum or iron floe can be separated by sedimentation or air flotation. Dissolved Air Flotation This process consists of saturating a portion of the wastewater feed, or some of the recirculated effluent from the flotation unit, with air at a gage pressure of 275 kPa to 415 kPa (40 psi to 60 psi). The wastewater or recycled effluent is held at this pressure for 1 minute to 5 minutes in a retention tank and then released at atmospheric pressure to the flotation chamber. The sudden reduction in pressure releases air bubbles less than 100 ym in diameter which attach themselves to the oil and sus- pended particles in the wastewater. The resulting agglomerates are then buoyed to the surface to form a froth layer which is removed by skimming devices. The retention time in the flotation chamber is usually 15 minutes to 40 minutes. The addition of flocculating agents, such as polyelectrolytes, often improves the effectiveness of the air flotation process and clarification. Coagulation Coagulation consists of adding chemicals to the wastewater to create fast-settling agglomerates or floes from finely divided and slow-settling particles. Chemical coagulation and sedimenta- tion can be used to treat the effluent from a gravity separator prior to biological treatment. The chemical coagulation-sedimentation process has three essen- tial steps. First, chemicals and/or polyelectrolytes are added in a flash mix tank for 1 minute to 3 minutes. Next, the waste- water is gently stirred in a flocculation basin for 10 minutes to 30 minutes so that floes grow large enough to settle readily. Finally, the agglomerated sludge is separated in a clarifier or settling basin. This process is capable of giving results com- parable to those of dissolved air flotation in removing oils, solids, BOD, and COD. When operated properly, dissolved air flotation with chemical coagulation can produce an effluent having an oil content of less 40 ------- than 10 g/m3. The reduction of organic pollutants may be inci- dental to the removal of oil and suspended solids. BOD5 reduc- tion can range from 20% to 70% (4). The effluent from flotation-coagulation systems or from primary settling may be further treated biologically in aerated lagoons, or by trickling filters, or by activated sludge. Some tank truck cleaners are trying biological treatment at the present time. Activated carbon adsorption is being used as an alternative to biological treatment. Aerated Lagoon Aerated biological treatment is achieved by mixing dilute concen- trations of microorganisms with wastewater in a large basin. The oxygen necessary to aerobically degrade the organic matter is supplied by mechanical or diffused aeration units, or by induced surface aeration. The turbulence normally maintained distributes the oxygen and biological solids throughout the basin. An aerated lagoon differs from an activated sludge unit in that the effluent from the aerated lagoon may not be settled prior to discharge, and the biological solids are not recirculated. The low rate of organic removal resulting from the low concentration of biological solids maintained in the lagoon requires a greater retention time for an equivalent reduction in BOD than is the case with activated sludge. An aerated lagoon is capable of removing 50% to 95+% of BODs, depending on temperature and pol- lutant treatability (4). The removal efficiencies may be improved by further treating the lagoon effluent using chemical coagulation, sedimentation, filtration, or an effluent polishing pond. Trickling Filter In this process, wastewater is passed through a porous bed (stones or plastic) that contains a fixed growth of microorgan- isms. A microbial film develops on the surface of the filtering medium and removes organic materials from the wastewater by adsorption, bioflocculation, and sedimentation. Oxygen is very important in this system (as it is in any aerobic biological system) for rapid metabolism of the removed organic matter. Since the filter medium has a large surface area, oxygen can move readily by simple diffusion from the void spaces into the liquid layer. Treatment rates of trickling filters are controlled by both hydraulic and organic loading rates. Stone trickling filters are limited, due to the low flow rates involved, to depths between 1 m and 3 m. Those using plastic generally have high hydraulic and organic loadings, and their bed depths range from 5 m to 12 m. A modification of the trickling filter, used at one treatment system visited, consists of a large, rotating, cylindrical cage, mounted horizontally and partially submerged, 41 ------- carrying plastic rings. The rotation of the cage constantly renews the oxygen and maintains a high trickle rate. As the microbial film ages and dies on the medium, it drops off and is washed away. With high organic and hydraulic loadings, the film growth is more rapid. However, the lack of oxygen in the medium interface coupled with greater hydraulic shearing action causes the microbial film to wash from the media surface continuously. A final clarifier is normally used to remove these solids from the filter effluent to maintain minimum effluent BOD and suspended solids concentration. Activated Sludge In this process, high concentrations (1.5 kg/m3 to 3 kg/m3) of newly grown and recycled microorganisms are suspended uniformly throughout a holding tank to which raw wastewaters are added. Oxygen is introduced by mechanical aerators, diffused air systems, or other means. The organic materials in the waste are removed from the aqueous phase by the microbiological growths and stabilized by biochemical synthesis and oxidation reactions. The basic activated sludge process involves the use of an aeration tank followed by a sedimentation tank. The flocculant microbial growths removed in the sedimentation tank are recycled to the aeration tank to maintain a high concentration of active micro- organisms. Although the microorganisms remove almost all of the organic matter from the waste being treated, much of the con- verted organic matter remains in the system in the form of micro- bial cells. These cells have a relatively high rate of oxygen demand and must be removed from the treated wastewater before it is discharged. Activated Carbon Adsorption This is one of the most effective methods for removing from wastewaters countless dissolved organic materials (both biode- gradable and refractory) which contribute to BOD, COD, and taste and odor problems. In a few existing units, biologically treated effluent is passed through vessels filled with granular, acti- vated carbon. In another unit visited, powdered activated carbon is added along with coagulation chemicals into a tank following biological treatment. It has been demonstrated in pilot units that raw wastes, which have been given chemical coagulation (with sedimentation or filtration) to remove suspended solids, can be processed by carbon adsorption to provide almost any level of treatment (20) . The carbon gradually loses its adsorptive capac- ity as it accumulates organic materials from the wastewater and must be eventually replaced. To make the process more economi- (20) Process Design Manual for Upgrading Existing Wastewater Treatment Plants. Contract 14-12-933, U.S. Environmental Protection Agency, October 1971. 42 ------- cal the spent carbon is usually reactivated and the bed replen- ished with new carbon. Frequently multiple adsorption colums are utilized in series or in .parallel so that at least one unit may be pulled out of service for replenishment. Moving bed carbon filters are sometimes used to eliminate the spare colums required for regeneration and to produce more consistent effluent, but there seem to be problems involved in the countercurrent movement of the carbon particles. Unlike biological treatment processes, the efficiency of carbon treatment is not very sensitive to seasonal temperature changes. In most cases, the combined use of coagulation, filtration, and carbon adsorption is more reli- able and controllable than biological treatment. Granular Media Filtration The media used in granular filters, either pressurized or grav- ity, may consist of 1) sand, 2) sand and coal, or 3) sand, coal, and a heavy fine material such as garnet. When the medium is sand, a relatively uniform grade of sand rests on a layer of coarser sand or fine gravel. When the medium is sand and coal, a layer of fine sand rests on a layer of medium coal. These two types of filters present the problem of keeping the fine sand from moving through the coarse layer to the bottom. This problem can usually be solved by placing a layer of garnet between the fine and coarse layers. This comprises the third medium listed above. Periodically, the top sand layer is removed for landfill- ing and is replaced with fresh sand. Granular media filters are capable of prodnr.tng an effluent which consistently shows extremely low suspended solids and oil content on the order of 5 g/m3 to 10 g/m3 for each (4). Batch Treatment of Individual Waste Streams Sometimes, wastes are encountered which are not effectively treated by the above processes or even interfere with them. Metals and cyanide wastes are examples. Normally they occur intermittently and in relatively small quantities, making them amenable to batch treatment prior to discharge to surface waters or before mixing with other wastes for further treatment. Chro- mium wastes, for example, can be treated with sulfuric acid and sulfur dioxide to reduce hexavalent chromium to trivalent, which can then be discharged for precipitation in the coagulation- sedimentation system described previously. Cyanides can be subjected to alkaline chlorination destruction. At one facility, phenol wastewaters are segregated and treated with ozone before discharge to the regular wastewater treatment system. Phenol concentrations are reduced from as high as 30 kg/m3 to less than 5 g/m3 (4). Ponds or Lagoons Wastewater treatment in ponds or lagoons is a common practice in the railroad industry and, to some degree, in the trucking 43 ------- industry. It may be preceded by any one of the above described methods although it most often follows gravity separation. Where practiced, ponding is ordinarily the final step in treatment. Ponds may be used for further gravity separation, for evapora- tion, or for aerobic digestion. Ponds are also used simply for equalization to eliminate slug discharges of pollutants to sur- face waters or to treatment facilities. The relatively long retention times provided assist in further oil separation and sedimentation, both of which are time dependent. Oil-skimming devices are used at the effluent outlet. Evaporation ponds which have no discharge are used effectively where the rate of evaporation exceeds the rate of precipitation by an amount equal to or greater than the rate at which waste- water is sent to the pond. Evaporation ponds are inadequate if some of the wastewater dissipates through ground seepage and contaminates groundwaters. Ponds have actually been designed to leak where the soil is porous but, generally, this is not con- sidered acceptable practice because of groundwater contamination possibilities. Ponds or lagoons may be used to provide for aerobic digestion of oxygen-demanding wastes. Atmospheric aeration may be sufficient if the pond has a large surface area and volume compared with waste concentration. If atmospheric aeration is not adequate, mechanical aeration may be used. Ponds may also be used for anaerobic decomposition of organic wastes, but grossly unpleasant odors and putrid conditions frequently result. Adequately designed ponds are capable of removing up to 95% of oil, suspended solids, BOD, and other constituents, depending on retention time, temperature, and treatability. Under ideal conditions, evaporation ponds can remove virtually 100% of all waste materials, leaving just solids to be incinerated or land- filled (4). Neutralization Neutralization, or pH adjustment to near the neutral value of 7.0, can be provided at any stage of treatment. Some microorgan- isms and treatment chemicals are somewhat pH sensitiver in which case pH control becomes mandatory. The adjustment of pH is accomplished by the addition of either acidic or basic chemicals, depending on the condition to be corrected. The hauling of acids and caustics, and the use of caustic or acid wash solutions, fre- quently necessitate pH control, even if only to meet regulatory limits on effluents. Table 23 summarizes reported effluent concentrations from various combinations of the above described systems for petroleum 44 ------- TABLE 23. LOWEST EFFLUENT CONCENTRATIONS EXPECTED USING VARIOUS TREATMENT PROCESS COMBINATIONS FOR PETROLEUM REFINERIES (21) Process API separator API separator and clarifier API separator and dissolved air flotation API separator and granular media filter API separator and oxidation pond BODs 250 45 45 40 10 Effluent concentration, g/m3 Suspended COD solids Oil Phenol 260 50 20 6 130 25 5 10 130 25 5 10 100 563 50 20 2 0.01 API separator and clarifier, dissolved air flotation, granular media filter, aerated lagoon API separator and trickling filter API separator and clarifier, dissolved air flotation, granular media filter, activated carbon 10 10 25 80 2,010 0.5 0.1 30 10 0.1 Note: Blanks indicate data not available. refiners (21). Wastewater composition could affect the effluents achieved. In general, a system which includes gravity separa- tion, dissolved air flotation, granular media filtration, and activated carbon adsorption is capable of producing a high quality effluent. However, carbon treatment is relatively costly and is not a cure-all for effluents. The above treatment systems are available to the drum cleaning industry, and some companies are attempting to use some of the processes for wastewater treatment. Ponds are used by some com- (21) Development Document for Proposed Effluent Limitations Guidelines and New Source Performance Standards for Petro- leum Refineries. Office of Enforcement and General Counsel, National Field Investigations Center, Cincinnati, Ohio, 1973. 45 ------- panies for sedimentation before sending the effluent to a munici- pal treatment system. Several companies have begun using closed systems for their washing cycles. In such systems, suspended solids are removed for landfilling, and the caustic liquor is regenerated and reused for long periods. When necessary, the liquid can be neutralized and discharged to the municipal system. Solid waste materials are universally either incinerated or land- filled. In some cases, it is possible for undesirable materials to be landfilled in such a condition as to be hazardous because of soil percolation. This should be prevented by careful control of landfill operations involving these wastes. FUTURE CONSIDERATIONS Air Closed, recycled washing systems for tank cars, tank trucks, and drums have very low, if any, air emissions. Drum burning fur- naces, when afterburners are operated properly, are capable of being controlled to meet most standards. Vapors from complete water flushing of tank cars and tank trucks used to haul vola- tile, combustible materials can be, and often are, sent to flares. Open cleaning operations, such as steaming of tank cars, tank trucks, and drums, and open air burning of drums are sources of uncontrolled air emissions. There are no feasible, or readily available, control methods known for these operations at the present time. Converting open cleaning operations to closed- cycle cleaning, and eliminating open air drum burning, seem to be the only alternatives for the immediate future. Water Existing control technology for wastewater treatment available to all three types of cleaning operations appears to be capable of providing adequate control of effluents (10). Further develop- ment in the area of effective strains of microorganisms for biological treatment of organic materials would be desirable. Economic considerations are a key factor in future applications of treatment technology. The development of standardized, building-block process units could lead to greater economy in capital costs for treatment facilities. Solid Incineration and landfilling of solid wastes are in fairly common usage at the present time. When properly done, these methods may be adequate for the future needs of tank car, tank truck, and drum cleaning. ------- SECTION 6 GROWTH POTENTIAL At present there is no practical, economical method for effec- tively reducing the emissions from rail tank car, tank truck, and drum cleaning. It is expected that the volume of chemical mater- ials transported will increase in parallel with the increase in chemical production. It has been forecast that chemical produc- tion will increase 9% in 1977, 7% in 1978, 5% in 1979, and 6% in 1980 for a total increase of 30% through 1980 (22). Therefore, emissions from these cleaning operations will increase by 30% also, unless some control methods are developed. Continued efforts by the cleaning companies to install and/or optimize wastewater treatment systems should result in a decrease (estimated 50%) in the amount of discharged water pollutants through 1980. (22) Outlook is Optimistic for Chemicals in 1977. Chemical and Engineering News, 54(48):6-7, 1976. 47 ------- REFERENCES 1. Analysis of Proposed EPA Effluent Limitations on the For- Hire Tank Truck Industry. National Tank Truck Carriers, Inc., Washington, B.C., June 1974. 31 pp. 2. Yearbook of Railroad Facts, 1973. Association of American Railroads, Washington, D.C., 1973. 3. Development Document for Proposed Effluent Limitations Guidelines and New Source Performance Standards for the Railroad Segment of the Transportation Industry Point Source Category. Office of Enforcement and General Counsel, National Field Investigations Center, Cincinnati, Ohio, February 1975. 4. Development Document for Proposed Effluent Limitations Guidelines and Source Performance Standards for the Trucking Segment of the Transportation Industry Point Source Category. Office of Enforcement and General Counsel, National Field Investigations Center, Cincinnati, Ohio, 1975. 5. Air Pollution Engineering Manual, Second Edition, J. A. Danielson, ed. Publication No. AP-40, U.S. Environ- mental Protection Agency, Research Triangle Park, North Carolina, May 1973. 987 pp. 6. Railway Age Directory of Contract Car Repair Facilities. Railway Age, 177(13):44-49, 1976. 7. Final Report on Cost of Implementation and Capabilities of Available Technology to Comply with P.L. 92-500; Volume IV: Industry Categories 29-38. Prepared for the National Commission on Water Quality by Battelle Columbus Labora- tories, Columbus, Ohio, July 3, 1975. 8. TLVs® Threshold Limit Values for Chemical Substances and Physical Agents in the Workroom Environment with Intended Changes for 1975. American Conference of Governmental Industrial Hygienists, Cincinnati, Ohio, 1975. 97 pp. / 9. Sax, N. I. Dangerous Properties of Industrial Materials, Third Edition. Reinhold Book Corporation, New York, New York, 1968. 1251 pp. 48 ------- 10. O'Brien, J. E. A Demonstration Plant for the Treatment of Waste Waters from Tank Truck Cleanings. Presented at the American Institute of Chemical Engineers National Meeting, Atlantic City, New Jersey, September 1, 1976. 8 pp. 11. Compilation of Air Pollutant Emission Factors, Second Edition. Publication No. AP-42, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, April 1973. p. 2.2-1. 12. Serth, R. W., and T. W. Hughes. Source Assessment: Phthalic Anhydride (Air Emissions). EPA-600/2-76-032d, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, December 1976. 154 pp. 13. Code of Federal Regulations, Title 42 - Public Health, Chapter IV - Environmental Protection Agency, Part 410 - National Primary and Secondary Ambient Air Quality Standards, April 28, 1971. 16 pp. 14. Eimutis, E. C., and R. P. Quill. Source Assessment: State- by-State Listing of Criteria Pollutant Emissions, EPA-600/ 2-77-107b, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina, July 1977. 146 pp. 15. Turner, D. B. Workbook of Atmospheric Dispersion Estimates Public Health Service Publication No. 999-AP-26, U.S. Department of Health, Education, and Welfare, Cincinnati, Ohio, 1969. 64 pp. 16. Decision Criteria for Water Discharges. Draft prepared for EPA review under Contract 68-02-1874 by Monsanto Research Corporation, Dayton, Ohio, 1976. 4 pp. 17. Eimutis, E. C., T. J. Hoogheem, and T. W. Hughes. Briefing Document: Water Source Severity and Initial Water Prioritization Structures. Draft prepared under EPA Contract 68-02-1874 by Monsanto Research Corporation, Dayton, Ohio, September 21, 1976. 12 pp. 18. Quality Criteria for Water. EPA-440/9-76-023, U.S. Environmental Protection Agency, Washington, D.C. 501 pp. 19. Manual on Disposal of Refinery Wastes. American Petroleum Institute, Washington, D.C., 1969. 20. Process Design Manual for Upgrading Existing Waste Water Treatment Plants. Contract 14-12-933, U.S. Environmental Protection Agency, October 1971. 49 ------- 21. Development Document for Proposed Effluent Limitations Guidelines and New Source Performance Standards for Petroleum Refineries. Office of Enforcement and General Counsel, National Field Investigations Center, Cincinnati, Ohio, 1973. 22. Outlook is Optimistic for Chemicals in 1977. Chemical and Engineering News, 54(48) :6-7, 1976. 50 ------- APPENDIX A ESTIMATES OF DRUM BURNING EMISSIONS PARTICULATES The particulate emission factor for auto incineration is 0.68 kg/car, based on 112 kg of combustible material (CM) on a stripped car body (11) . Assuming 2 kg of combustible material per drum gives: E = 0-68 kg t car . 2 kg CM p car * 112 kg CM * drum = 0.012 kg/drum A large representative plant cleans 400,000 drums/yr of which 65% are burned. Thus, 260,000 drums/yr are burned, and assuming 260 days/yr of operation, 24 hr/day gives: Therefore, Q = 0.012 -2- . 0.012 . -- . p drum s = 0.00014 kg/s or 0.14 g/s where Q = mass particulate emission rate, g/s NITROGEN OXIDES (NO ) X Following the same logic as above: = o 01 -. • , , 0 _ - 2kg_CM = 1Q-, k /drum iNO car 112 kg CM drum y/ J^. A large representative plant burns 0.012 drum/s; therefore Q Q = 1.8 x I0~k kg/drum • 0.012 drum/s = 2.2 x 10~6 kg/s or 2.2 x 10~3 g/ 51 s ------- DERIVATION OF REPRESENTATIVE DRUM CLEANING PLANTS There are two types of plants: those which wash and burn drums clean and those which only wash drums clean. Using NBADA data on drums burned and washed (Table 11), the average size of the two types of plants can be derived. There are 9,090,000 drums burned clean at 35 facilities, for an average of 2-60,000 drums per facility. Assuming that 65% of the drums handled by these facilities require burning and that the remaining 35% can be cleaned by washing, the average facility handles 400,000 drums per year. The remaining 98 facilities wash drums only and handle the remaining 8,200,000 drums per year. The facilities which wash clean only are much smaller with an average of 84,000 drums per year for NBADA members. A representa- tive plant which washes only would be even smaller if the total number of facilities were considered. For purposes of this report, the larger size is chosen. Thus, the representative plants are: Burning and washing - 400,000 drums/yr Washing only , - 84,000 drums/yr ESTIMATION OF DRUM CLEANING EFFLUENTS Using tank truck cleaning effluent data, drum cleaning was esti- mated as follows. For 30 tank trucks per day, 45.4 m3/day (12,000 gal/day) of effluent are produced when removing 100 kg of material per truck. For oil and grease, this gives 230 g/m3 in the effluent, or 10.4 kg/day. This is 3.48 g of oil and grease per kilogram of material removed. Since each drum contains 2 kg of waste, the oil and grease are estimated as 6.96 g per drum washed. For the representative plants, this means: 35% of Type a plants - 0.97 metric tons/yr 100% of Type b plants - 0.585 metric tons/yr Assuming 260 days of operation per year gives: Type a plant - 3.75 kg/day Type b plant - 2.25 kg/day Estimated flow rates (from plant personnel) of 25 m3/day (6,600 gal/day) and 15 m3/day (4,000 gal/day) for Type a and Type b plants, respectively, gives effluent concentrations as follows: Type a plant - 148 g/m3 Type b plant - 148 g/m3 Other effluents are calculated in a similar manner. 52 ------- APPENDIX B DEFINITION OF SOURCE SEVERITY FOR WATER DISCHARGES AND CALCULATION OF RIVER OR END-OF-PIPE CONCENTRATIONS Source severity is defined as the pollutant concentration to which aquatic life is exposed divided by an acceptable concen- tration. The "exposure" concentration is the fully diluted receiving water concentration resulting from the effluent of the specific discharge of concern. The "acceptable" concentra- tion (F) is defined as that concentration at which it is assumed that an incipient adverse environmental impact occurs. For most pollutants, it is the water quality criteria. For pollutants without water quality criteria, F is the lowest value of the following concentrations: 0.01 LCso (LCso is the lethal concentration of a pollutant to 50% of an aquatic life exposed to the pollutant) 0.00225 LD50 (LD50 is the lethal dose of a pollutant to 50% of a male rat population) Mathematically, source severity (S) is: s _(VVR CD) b " F where V^, V_, = volume of discharge and river flow, respectively D R C = concentration of discharge F = acceptable concentration as defined above The oxygen source severity is defined as the maximum mass of oxygen that can potentially be consumed by a specific discharge divided by the mass of oxygen in the receiving water that can be consumed without exceeding the minimum "water quality criteria for dissolved oxygen. The maximum mass of oxygen potentially consumable by the discharge is defined as the total oxygen demand (TOD) concentration multiplied by the discharge flow rate. The "allowable" mass is defined as the receiving water volumetric flow rate of mixing zone volume multiplied by the difference between the saturation concentration (Cg) at 10 °C and the minimum water quality criteria for dissolved oxygen 53 ------- Hence, the source severity can be defined mathematically as: ^ITOD s = CS - D°(WQC) The receiving water is assumed to be initially at saturation and the discharge is assumed to be fully diluted and mixed upon enter- ing the receiving water. It is also assumed that all of the total oxygen demand occurs instantaneously with no reaearation of the receiving body of water. If it is desired to evaluate the severity at any other river flow rate, severity can be calculated as follows: So = S where Sj = standard source severity as shown in Table 19 82 = source severity at river flow rate, V^ VR VR = river flow rates corresponding to the 2 lf 2 source severities S\ and 82, respectively In addition, the concentration expected in the river can be determined by multiplying the source severity and the hazard factor (Table 18). The concentration expected from the discharge, CD (no dilution in the river, can be calculated using the follow- ing set of equations: CD = SD F where and S = severity from Table 19 V0 = river flow in Equation 3, 856 m3/s R » V = volumetric discharge, m3/s F = hazard factor from Table 18 54 ------- GLOSSARY affected population: Number of nonplant persons exposed to concentrations of airborne materials which are present in concentrations greater than a determined hazard potential factor. biochemical oxygen demand: A measure of the amount of oxygen consumed in the biological processes that break down organic matter in water. chemical oxygen demand: A measure of the amount of oxygen required to oxidize organic and oxidizable inorganic compounds in water. criteria pollutants: Emission species for which ambient air quality standards have been established; these include particulates, sulfur oxides, nitrogen oxides, carbon monoxide, and nonmethane hydrocarbons. dedicated: Type of car, truck or drum used for carrying one commodity only and, unless contaminated, cleaned only prior to repair or testing. emulsion: A heterogeneous liquid mixture not normally miscible, held in suspension by agitation or certain additives. hazard factor: The ambient air quality standard of a criteria pollutant or a "corrected" TLV for noncriteria pollutants. national emissions burden: The total quantity of specific pollutants generated in the U.S. noncriteria pollutants: Emission species for which no ambient air quality standards have been established. nondedicated: Type of car, truck or drum which is cleaned after every use to prevent cross contamination. pollutant: Any introduced gas, liquid, or solid that makes a resource unfit for a specific purpose. representative source: A source whose performance characteris- tics are representative of those of a large number of actual sources of similar type and function. 55 ------- source severity: An indication of the hazard potential of a pollution source. i state emission burden: The total quantity of specific pollutants generated in a specific state. threshold limit value: Airborne concentrations of substances that represent conditions under which it is believed that nearly all workers may be repeatedly exposed day after day without adverse effect. total oxygen demand: A quantitative measure of all oxidizable material in water or wastewater as determined by measuring the depletion of oxygen in a known gas stream. turbidity: A cloudy condition in water due to the suspension of silt or finely divided organic matter. water quality criteria: The level of pollutants that affect the suitability of water for a given use. water quality standard: A plan for water quality management containing four major elements: the use to be made of the water; criteria to protect those uses; implementation plans and enforcement plans; and an antidegradation statement to protect existing high quality waters. ------- .„ , TECHNICAL REPORT DATA (flease read Instructions on the rtvtnt btfore completing) . REPORT NO. f EPA-600/2-78-004g 4. TITLE AND SUBTITLE SOURCE ASSESSMENT: RAIL TANK CAR, TANK TRUCK, AND DRUM CLEANING, State of the Art 3. RECIPIENT'S ACCESSION NO. 6. REPORT DATE .April 1978 issuing date 0. PERFORMING ORGANIZATION CODE 7. AUTHORIS) ' ' — D. E. Barley, K. M. Tackett and T. R. Blackwood a. PERFORMING ORGANIZATION REPORT NO. MRC-DA-713 9. PERFORMING ORGANIZATION NAME AND ADDRESS Monsanto Research Corporation 1515 Nicholas Road Dayton., Ohio 45407 10. PROGRAM ELEMENT NO. 1AB604 11. CONTRACT/GRANT NO. 68-02-1874 13. SPONSORING AGENCV NAME AND ADDRESS Industrial Environmental Research Laboratory-cin., OH Office of Research and Development U.S. Environmental Protection Agency Cincinnati. Ohio 45268 ; 13. TYPE OF REPORT AND PERIOD COVERED Task Final 8/76-9/77 14. SPONSORING AGENCV CODE EPA/600/12 15. SUPPLEMENTARY NOTES IERL-Ci project leader for this report is R. J. Turner, 513-684-4481. 16. ABSTRACT _ __________________________________ This document reviews the state of the art of air emissions and water pollutants from cleaning rail tank cars, tank trucks, and drums. Compo- sition, quantity, and rate of emissions and pollutants are described. Rail tank cars, tank trucks, and drums are used to transport chemical and petroleum commodities from producer to consumer. Steaming, washing and/or flushing of such units result in air emissions and wastewater effluents. Air emissions are predominantly organic chemical vapors. Water pollut- ants common to these operations are primarily oil and grease, COD, BOD, suspended solids and many other organic and inorganic materials. Representative sources were defined in order to evaluate the hazard poten- tial. Source severity was defined and evaluated for air emissions and for wastewater effluents. Control methods used to reduce emissions from rail tank car and tank truck cleaning consist only of flaring flushed gases. By EPA estimates, two-thirds of the tank truck industry dis- charges into municipal systems with little or no pretreatment. This treatment has generally been limited to sedimentation, neutralization, evaporation ponds, and lagoons. 17. KEY WORDS AND DOCUMENT ANALYSIS DESCRIPTORS Air Pollution Water Pollution Assessments b.lDENTIFIERS/OPEN ENDED TERMS Air Pollution Control Water Pollution Control Source Assessment COSATi Field/Group 68A 8. DISTRIBUTION STATEMENT Release to Public 19. SECURITY CLASS IThti Report/ Unclassified 21. NO. OF PAGES 20. SECURITY CLASS (This page I Unclassified 22. PRICE EPA Form 2*20-1 (t-73) 57 * U.S. MVEMMBIT PRINTING OFFICE 197»—260-880/38 ------- |