Appendix A  Example NAICS & SIC codes for MP& M Sectors Appendix A EXAMPLE NAICS AND SIC CODES FOR THE METAL PRODUCTS & MACHINERY FINAL EFFLUENT LIMITATIONS GUIDELINES AND STANDARDS Appendix A  Example NAICS & SIC codes for MP& M Sectors Appendix A Example NAICS and SIC codes for the Metal Products & Machinery Final Effluent Limitations Guidelines and Standards The scope of the MP& M regulation includes facilities that discharge process wastewater from oily operations and manufacture, maintain, or rebuild metal parts, products, or machines used in the following sectors: Aerospace, Aircraft, Bus & Truck, Electronic Equipment, Hardware, Household Equipment, Instruments, Mobile Industrial Equipment, Motor Vehicles, Office Machines, Ordnance, Precious Metals and Jewelry, Railroad, Ships and Boats, Stationary Industrial Equipment, and Miscellaneous Metal Products. In addition, state, local and federal government facilities that discharge wastewater from oily operations and manufacture, maintain, or rebuild metal parts, products or machines ( e. g., a town that operates its own bus, truck, and/ or snow removal equipment maintenance facility) are also covered by the MP& M rule.

EPA also evaluated job shops and printed wiring board facilities for the final rule ( see Section 6.0). As described in Section 9.0, these facilities are not regulated by the MP& M effluent guidelines.

Table A 1 lists of example Standard Industrial Classification ( SIC) codes and North American Industrial Classification System ( NAICS) codes associated with the various MP& M industrial sectors and the two industrial sectors also reviewed for the final rule. Please note that this list is not intended to be exhaustive, but rather it provides a guide regarding entities that may be within the scope of the MP& M industry.

Table A 1 Example SIC and NAICS Codes Associated with MP& M Industrial Sectors Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Aerospace 33641400 3761 Guided Missiles and Space Vehicles 33641500 3764 Guided Missile and Space Vehicle Propulsion 33641900 3769 Other Space Vehicle and Missile Parts A 1 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Aircraft 33641100 3721 Aircraft 33641200 3724 Aircraft Engines and Engine Parts 33641300 33291220 33399520 33399620 3728 Aircraft Parts and Auxiliary Equipment 48811110 48811910 48819000 56172020 4581 Airports, Flying Fields, Airport Terminal Services Bus And Truck 33621120 3713 Truck and Bus Bodies 33621200 3715 Truck Trailers 48511100 48511200 48511300 48511900 4111 Local and Suburban Transit 48532000 48541020 48599100 48599920 62191090 4119 Local Passenger Transit, N. E. C.

48521000 4131 Intercity and Rural Bus Transportation 48551010 4141 Local Bus Charter Service 48551020 4142 Bus Charter Service, Except Local 48849010 4173 Bus Terminal and Service Facilities 48411010 48411020 4212 Local Trucking without Storage 48412100 48412200 48421020 4213 Trucking, Except Local 48411030 48411040 4214 Local Trucking with Storage A 2 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Bus and Truck ( Continued)

49211010 49221000 4215 Courier Services, Except by Air 48849020 4231 Trucking Terminal Facilities Electronic Equipment 33421000 3661 Telephone and Telegraph Apparatus 33422010 3663 Radio and Television Broadcast and Communications Equipment 33429000 3669 Communications Equipment, N. E. C.

33441100 3671 Electron Tubes 33441400 3675 Electronic Capacitors 33441610 33441620 3677 Electronic Coils and Transformers 33441700 3678 Connectors for Electronic Applications 33422020 33441820 33441900 33632210 3679 Electronic Components, N. E. C.

33451010 33451110 33451610 33451910 33512920 33599920 33911410 3699 Electrical Machinery, Equipment, and Supplies, N. E. C.

Hardware 32312220 2796 Platemaking and Related Services 33281100 3398 Metal Heat Treating 33243910 3412 Metal Shipping Barrels, Drums, Kegs, Pails 33221110 3421 Cutlery 33221210 33221240 3423 Hand and Edge Tools, Except Machine Tools and Handsaws 33221300 3425 Hand Saws and Saw Blades 33243920 3429 Hardware, N. E. C.

A 3 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Hardware ( Continued)

33341410 3433 Heating Equipment, Except Electric and Warm Air Furnace 33231210 3441 Fabricated Structural Metal 33231300 3443 Fabricated Plate Work ( Boiler Shops)

33243930 3444 Sheet Metal Work 33232310 3446 Architectural and Ornamental Metal Work 33231100 3448 Prefabricated Metal Buildings and Components 33231220 3449 Miscellaneous Metal Work 33272100 3451 Screw Machine Products 33272200 3452 Bolts, Nuts, Screws, Rivets, and Washers 33211100 3462 Iron and Steel Forgings 33211500 3466 Crowns and Closures 33221400 3469 Metal Stamping, N. E. C.

33291210 3492 Fluid Power Valves and Hose Fittings 33261100 3493 Steel Springs 33291920 3494 Valves and Pipe Fittings, Except Brass 33451810 3495 Wire Springs 33261830 3496 Miscellaneous Fabricated Wire Products 33299620 3498 Fabricated Pipe and Fabricated Pipe Fitting 33243940 33251020 33211700 33721540 33991420 3499 Fabricated Metal Products, N. E. C.

33351210 3541 Machine Tools, Metal Cutting Types 33351300 3542 Machine Tools, Metal Forming Types 33351400 3544 Special Dies and Tools, Die Sets, Jigs and Fixtures, and Industrial Molds 33351500 3545 Machine Tool Access and Measuring Devices 33399100 3546 Power Driven Hand Tools 33999320 3965 Fasteners, Buttons, Needles, Pins A 4 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Household Equipment 33712400 2514 Metal Household Furniture 33721400 2522 Office Furniture, Except Wood 33712710 2531 Public Building and Related Furniture 33721530 2542 Partitions and Fixtures, Except Wood 33792000 2591 Drapery Hardware and Window Blinds/ shades 33712720 33911310 2599 Furniture and Fixtures, N. E. C.

33299800 3431 Metal Sanitary Ware 33291300 3432 Plumbing Fittings and Brass Goods 33232120 3442 Metal Doors, Sash, and Trim 33522100 3631 Household Cooking Equipment 33522200 3632 Household Refrigerators and Home and Farm and Freezers 33522400 3633 Household Laundry Equipment 33521100 33341420 3634 Electric Housewares and Fans 33521210 3635 Household Vacuum Cleaners 33521220 33522800 3639 Household Appliances, N. E. C.

33511000 3641 Electric Lamps 33593100 3643 Current Carrying Wiring Devices 33593200 3644 Noncurrent Carrying Wiring Devices 33512120 3645 Residential Electrical Lighting Fixtures 33512200 3646 Commercial, Industrial, and Institutional 33512910 3648 Lighting Equipment, NEC 33431000 3651 Radio/ Television Sets Except Communication Types 81131030 81141220 7623 Refrigeration and Air conditioning Service and Repair Shops A 5 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Instruments 33451120 3812 Search, Detection, Navigation, Guidance, Aeronautical, Nautical Systems and Instruments 33911100 3821 Laboratory Apparatus and Furniture 33451200 3822 Automatic Environmental Controls 33451300 3823 Process Control Instruments 33451400 3824 Fluid Meters and Counting Devices 33451500 3825 Instruments to Measure Electricity 33451620 3826 Laboratory Analytical Instruments 33331420 3827 Optical Instruments and Lenses 33451920 3829 Measuring and Controlling Devices, N. E. C.

33911210 33911220 3841 Surgical and Medical Instruments and Apparatus 32229120 33451020 33911320 3842 Orthopedic, Prosthetic and Surgical Supplies 33911420 3843 Dental Equipment and Supplies 33451700 3844 X ray Apparatus and Tubes 33451030 3845 Electromedical Equipment 33911500 3851 Ophthalmic Goods 81121210 81121310 81121910 81141120 81141210 7629 Electric Repair Shop Job Shopsa 33281300 3471 Plating and Polishing 33281200 33991210 33991410 3479 Metal Coating and Allied Services A 6 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Mobile Industrial Equipment 33221220 33311100 33392210 3523 Farm Machinery and Equipment 33221230 33311200 3524 Garden Tractors and Lawn and Garden Equipment 33312000 33392310 33651010 3531 Construction Machinery and Equipment 33313100 3532 Mining Machinery and Equipment, Except Oil Field 33392320 3536 Hoists, Industrial Cranes and Monorails 33243950 33299960 33392400 3537 Industrial Trucks, Tractors, Trailers 33699220 3795 Tanks and Tank Components Motor Vehicle 33637000 3465 Automotive Stampings 33631100 3592 Carburetors, Piston Rings, Valves 33632100 3647 Vehicular Lighting Equipment 33632220 3694 Electrical Equipment for Motor Vehicles 33611100 33611200 33612000 33621110 33621130 33699210 3711 Motor Vehicle and Automobile Bodies 33621130 3714 Motor Vehicle Parts and Accessories 33621300 3716 Mobile Homes 33699110 3751 Motorcycles 33621410 3792 Travel Trailers and Campers 33699900 3799 Miscellaneous Transportation Equipment 48531000 4121 Taxicabs 44131030 5013 Motor Vehicle Supplies and New Parts A 7 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Motor Vehicle ( Continued)

44111000 5511 Motor Vehicle Dealers ( New and Used)

44112000 5521 Motor Vehicle Dealers ( Used Only)

44121000 5561 Recreational Vehicle Dealers 44122100 5571 Motorcycle Dealers 44122900 5599 Automotive Dealers, N. E. C.

53211200 7515 Passenger Car Lease 81112110 81112120 81112130 7532 Top, Body, and Upholstery Repair and Paint Shops 81111200 7533 Auto Exhaust Systems 81111300 7537 Auto Transmission Repair 81111100 7538 General Automotive Repair 81111810 81111820 81111830 81111840 81111890 7539 Auto Repair Shop, N. E. C.

81119100 81119820 7549 Auto Services, Except Repair and Carwashes Office Machines 33411100 3571 Electronic Computers 33411200 3572 Typewriters 33411300 3575 Computer Terminals 33411910 3577 Computer Peripheral Equipment, N. E. C.

33411920 3578 Calculating, Accounting Machines Except Computers 33451820 3579 Office Machines, N. E. C.

81121230 7378 Computer Maintenance and Repairs 54151220 54151910 33451820 7379 Computer Related Services, N. E. C.

A 8 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Ordnance 33299200 3482 Small Arms Ammunition 33299300 3483 Ammunition, Except for Small Arms 33299400 3484 Small Arms 33299500 3489 Ordnance and Accessories, N. E. C.

Precious Metals and Jewelry 33451830 3873 Watches, Clocks, and Watchcases 33991120 3911 Jewelry, Precious Metal 33991220 3914 Silverware, Plated Ware and Stainless 33991300 3915 Jewelers' Materials and Lapidary Work 33991430 3961 Costume Jewelry 81149010 7631 Watch, Clock, Jewelry Repair Printed Circuit Boardsa 33441200 3672 Printed Circuit Boards Railroad 33391120 33651020 3743 Railcars, Railway Systems 48211100 4011 Railroad Transportation 48211200 4013 Railroad Transportation Ships and Boats 33661100 3731 Ship Building and Repairing 33661200 81149020 3732 Boat Building and Repairing 48311100 4412 Deep Sea Foreign Transportation 48311310 4424 Deep Sea Domestic Transportation 48311320 4432 Freight Transportation Great Lakes 48321110 4449 Water Transportation of Freight, N. E. C.

48311410 4481 Deep Sea Passenger Transportation 48311420 4482 Ferries A 9 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Ships and Boats ( Continued)

48321220 48721010 4489 Water Passenger Transportation, N. E. C.

48831010 4491 Marine Cargo Handling 48321120 4492 Towing and Tugboat Service 71393000 4493 Marinas 48831020 48833020 48833030 48839010 53241110 4499 Water Transportation Services, N. E. C.

Stationary Industrial Equipment 33361100 3511 Steam, Gas, Hydraulic Turbines, Generating Units 33639910 3519 Internal Combustion Engines, N. E. C.

33313200 3533 Oil Field Machinery and Equipment 33392100 3534 Elevators and Moving Stairways 33392220 3535 Conveyors and Conveying Equipment 33299700 3543 Industrial Patterns 33351600 3547 Rolling Mill Machinery and Equipment 33399210 3548 Electric and Gas Welding and Soldering 33351800 3549 Metal Working Machinery, N. E. C.

33329210 3552 Textile Machinery 33321000 3553 Woodworking Machinery 33329100 3554 Paper Industries Machinery 33329310 3555 Printing Trades Machinery and Equipment 33329400 3556 Food Products Machinery 33329810 3559 Special Industry Machinery, N. E. C.

33391110 3561 Pumps and Pumping Equipment 33299100 3562 Ball and Roller Bearings 33391200 3563 Air and Gas Compressors A 10 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Stationary Industrial Equipment ( Continued)

33341200 33341100 3564 Blowers and Exhaust and Ventilation Fans 33399300 3565 Industrial Patterns 33361200 3566 Speed Changers, High Speed Drivers and Gears 33399400 3567 Industrial Process Furnaces and Ovens 33361300 3568 Mechanical Power Transmission Equipment, N. E. C.

33399910 3569 General Industrial Machinery, N. E. C.

33331100 3581 Automatic Merchandising Machines 33331200 3582 Commercial Laundry Equipment 33639100 3585 Refrigeration and Air and Heating Equipment 33391300 3586 Measuring and Dispensing Pumps 33331920 3589 Service Industry Machines, N. E. C.

33399510 3593 Fluid Power Cylinders and Actuators 33399610 3594 Fluid Power Pumps and Motors 33399700 3596 Scales and Balances, Except Laboratory 33399920 3599 Machinery, Except Electrical, N. E. C.

33531120 3612 Transformers 33531300 3613 Switchgear and Switchboard Apparatus 33531210 3621 Motors and Generators 33599910 3629 Electric Industrial Apparatus, N. E. C.

53241210 7353 Heavy Construction Equipment Rental, Leasing 53221000 53229990 53231000 53241190 53241290 53242010 53249020 56299120 7359 Equipment Rental, Leasing, N. E. C.

A 11 Appendix A  Example NAICS & SIC codes for MP& M Sectors Table A 1 ( Continued)

Example NAICS and SIC Codes for the MP& M Industrial Sectors NAICS Code SIC Code Standard Industrial Classification Groups Miscellaneous Metal Products 33299940 3497 Metal Foil and Leaf 33331520 3861 Photographic Equipment and Supplies 33999200 3931 Musical Instruments 33699120 3944 Games, Toys, Children's Vehicles 33992000 3949 Sporting and Athletic Goods, N. E. C.

33994100 3951 Pens and Mechanical Pencils 33994300 3953 Marking Devices 33995000 3993 Signs and Advertising Displays 33999500 3995 Burial Caskets 33221270 33299980 33512130 3999 Manufacturing Industries, N. E. C.

81149030 7692 Welding Repair 48839030 81149090 56162200 56179010 81121220 81121990 81131010 81141110 81141290 7699 Repair Shop, Related Service Continuous Electroplaters 33281300 3399 Electroplating, Plating, Polishing, Anodizing, and Coloring Source: U. S. Census Bureau, North American Industrial Classification System, http:// www. census. gov/ epcd/ www/ naics. html. N. E. C.  Not elsewhere classified. a Industrial sector considered, but not included, in Part 438.

A 12 Appendix B  Analytical Methods and Baseline Values Appendix B ANALYTICAL METHODS AND BASELINE VALUES FOR THE METAL PRODUCTS AND MACHINERY INDUSTRY Appendix B  Analytical Methods and Baseline Values APPENDIX B ANALYTICAL METHODS AND BASELINE VALUES B. 1 Nominal Quantitation Limits B. 2 Baseline Values B. 3 Analytical Results Reporting Conventions B. 4 Analytical Methods B. 4.1 EPA Methods 1624, 1625, 1664, and OIA 1677 ( Volatile Organics, Semivolatile Organics, SGT HEM, HEM, and Available Cyanide) B. 4.2 EPA Methods 1620 and 200.7 ( Metals) B. 4.3 EPA Method 335.1 ( Amenable Cyanide) B. 4.4 EPA Methods 350.2 and 350.3 ( Ammonia as Nitrogen) B. 4.5 EPA Method 405.1 and SM 5210B ( BOD5 and Carbonaceous BOD) B. 4.6 EPA Methods 410.1, 410.2, and 410.4 ( Chemical Oxygen Demand) B. 4.7 EPA Method 325.3 ( Chloride) B. 4.8 EPA Method 340.2 ( Fluoride) B. 4.9 EPA Method 218.4, SM 3111A, and SM 3500D ( Hexavalent Chromium) B. 4.10 EPA Method 150.1 and SM 4500H ( pH) B. 4.11 EPA Methods 375.2 and 375.4 ( Sulfate) B. 4.12 EPA Methods 335.2 and 335.3 ( Total Cyanide) B. 4.13 EPA Method 160.1 and SM 2540C ( Total Dissolved Solids) B. 4.14 EPA Method 351.3 ( Total Kjeldahl Nitrogen) B. 4.15 EPA Method 415.1 ( Total Organic Carbon) B. 4.16 EPA Methods 420.1 and 420.2 ( Total Phenols) B. 4.17 EPA Methods 365.2 and 365.3 ( Total Phosphorus) B. 4.18 EPA Methods 376.1 and 376.2, SM 4500D and SM 4500E, and D4658 ( Total Sulfide) B. 4.19 EPA Method 160.2 and SM 2540D ( Total Suspended Solids) B. 4.20 EPA Methods 204.1 and 7041 ( Antimony) B. 4.21 EPA Methods 206.2 and 7060A ( Arsenic) B. 4.22 EPA Method 231.2 ( Gold) B. 4.23 EPA Method 239.1 ( Lead) B. 4.24 EPA Methods 245.1 and 245.2 ( Mercury) B. 4.25 EPA Method 265.2 ( Rhodium) B. 4.26 EPA Methods 270.2 and 7740 ( Selenium) B. 4.27 EPA Method 272.1 ( Silver) B. 4.28 EPA Methods 279.1 and 7841 ( Thallium) B. 4.29 EPA Methods 624 and 625 ( Volatile Organics and Semivolatile Organics) B. 4.30 EPA Method 630.1 ( Ziram) B. 5 Analytical Method Development Efforts i Appendix B  Analytical Methods and Baseline Values The analytical methods described in this appendix were used to determine pollutant levels in wastewater samples collected by EPA and industry at a number of metal products and machinery facilities. ( Sampling efforts are described in Section 3.0) In developing the rule, EPA used data from samples collected by EPA and industry to determine the levels of amenable cyanide, ammonia as nitrogen, available cyanide, biochemical oxygen demand ( BOD), carbonaceous biochemical oxygen demand, chemical oxygen demand ( COD), chloride, fluoride, hexavalent chromium, metals, oil and grease ( measured as hexane extractable material ( HEM)), pH, semivolatile organics, silica gel treated hexane extractable material ( SGT HEM), sulfate, total cyanide, total dissolved solids ( TDS), total Kjeldahl nitrogen ( TKN), total organic carbon ( TOC), total phenols, total phosphorus, total sulfide, total suspended solids ( TSS), volatile organics, and ziram. As explained in Section 7.0, EPA is regulating a subset of these pollutants.

Sections B. 1 and B. 2 of this appendix provide explanations of nominal quantitation limits and baseline values. Section B. 3 describes the reporting conventions used by laboratories in expressing the results of the analyses. Section B. 4 describes each analytical method and the corresponding baseline values that EPA used in determining the pollutants of concern. Section B. 5 discusses analytical method development efforts. Table B 1 identifies the analytical methods and baseline values for each pollutant, identifies each pollutant by Chemical Abstract Service Registry Number, indicates whether the samples were collected by EPA and/ or by industry, and lists the nominal quantitation value for the method used.

Nominal Quantitation Limits The nominal quantitation limit is the smallest quantity of an analyte that can be reliably measured with a particular method, using the typical ( nominal) sample size. The protocols used for determination of nominal quantitation limits in a particular method depend on the definitions and conventions that EPA used at the time the method was developed. The nominal quantitation limits associated with the methods addressed in this section fall into three categories.

1) The first category pertains to EPA Methods 1624, 1625, 1664, and OIA 1677, which define the minimum level ( ML) as the lowest level at which the entire analytical system must give a recognizable signal and an acceptable calibration point for the analyte. These methods are described in Section B. 4.1.

2) The second category pertains specifically to EPA Method 1620, and is explained in detail in Section B. 4.2.

3) The third category pertains to the remainder of the chemical methods in which a variety of terms are used to describe the lowest level at which measurement results are quantitated. In some cases ( especially with the classical wet chemistry analytes) the methods date to the 1970s and 1980s when different concepts of quantitation were employed by EPA. These methods typically list a measurement range or lower limit of B 1 B. 1 Appendix B  Analytical Methods and Baseline Values measurement. The terms differ by method and, as discussed in subsequent sections, the levels presented are not always representative of the lowest levels laboratories currently can achieve.

For those methods associated with a calibration procedure, the laboratories demonstrated through a low point calibration standard that they were capable of reliable quantitation at method specified ( or lower) levels. In such cases these nominal quantitation limits are operationally equivalent to the ML ( though not specifically identified as such in the methods).

In the case of titrimetric or gravimetric methods, the laboratory adhered to the established lower limit of the measurement range published in the methods. Details of the specific methods are presented in Sections B. 4.3 through B. 4.30.

Baseline Values As described further in Section 7.0, in determining the pollutants of concern, EPA compared the reported concentrations for each pollutant to a multiple of the baseline value. As described in Section B. 3 and shown in Table B 1, for most pollutants, the baseline value was set equal to the nominal quantitation limit for the analytical method. EPA made two general types of exceptions which are briefly described below. Section B. 4 provides additional details about these exceptions in the context of the analytical methods.

The first type of exception was for baseline values that were different than the nominal quantitation limits in the analytical methods. When the baseline values were lower, EPA made these exceptions because the laboratory submitted data that demonstrated that reliable measurements could be obtained at lower levels for those pollutants. When the baseline values were higher, EPA concluded that the nominal quantitation limit for a specified method was less than the level that laboratories could reliably achieve and adjusted the baseline value upward.

The second type of exception was for baseline values set at a common value for multiple analytical methods for the same pollutant. For some analytes, EPA permitted the laboratories to choose between methods to accommodate sample characteristics and/ or industry used a different analytical method than EPA. When these methods had different nominal quantitation limits, EPA generally used the one with the lowest value or the one associated with the method used for most samples.

B 2 B. 2 Appendix B  Analytical Methods and Baseline Values B. 3 Analytical Results Reporting Conventions The laboratories reported each analytical result either as a numeric value or as not quantitated1 . A numeric result indicates that the pollutant was quantitated2 in the sample. Most analytical results were reported as liquid concentrations in weight/ volume units ( e. g., micrograms per liter ( µ g/ L)), except for the pH data, which were reported in " standard units" ( SU). For solid samples, the results were provided in weight/ weight units ( e. g., milligrams per kilogram ( mg/ kg)). In those instances, EPA converted the solids results into weight/ volume units by using a conversion factor based on the percentage of solids in the samples.

For example, the result for a hypothetical pollutant X would be reported as " 15 g/ L" when the laboratory cannot quantitated the amount of pollutant X in the sample as being 15 g/ L. When the laboratory cannot quantitate the amount of pollutant X in the sample, the laboratory would report that the analytical result indicated a value less than the sample specific quantitation limit of 10 g/ L ( i. e., "< 10 g/ L"). The actual amount of pollutant X in that sample is between zero ( i. e., the pollutant is not present) and 10 g/ L. The sample specific quantitation limit for a particular pollutant is generally the smallest quantity in the calibration range that can be measured reliably in any given sample. Reporting a pollutant as nonquantitated does not mean that the pollutant is not present in the wastewater; it merely indicates that analytical techniques ( whether because of instrument limitations, pollutant interactions, or other reasons) do not permit its measurement at levels below the sample specific quantitation limit.

In its calculations, EPA generally substituted the reported sample specific quantitation limit for each nonquantitated result. As described in Section B. 4.1, EPA substituted the baseline value for the nonquantitated result when the sample specific quantitation limit was less than the baseline value. In addition, when the detected quantitated value was below the baseline value, EPA substituted the baseline value for the measured value and considered these values to be nonquantitated in the statistical analyses.

B. 4 Analytical Methods EPA and industry analyzed all metal products and machinery facility wastewater samples using methods identified in Table B 1. ( As explained in Section 7.0, EPA is regulating only a subset of these analytes.) In analyzing samples, EPA generally used analytical methods approved at 40 CFR 136 or methods that EPA has used for decades in support of effluent guidelines development. Exceptions for use of nonapproved methods are explained in the method specific subsections that 1Elsewhere in this document and in the preamble to the rule, EPA may refer to pollutants as   not detected  or   nondetected.  This appendix uses the terms   not quantitated  or   nonquantitated  rather than not detected or nondetected.

2Elsewhere in this document and in the preamble to the rule, EPA may refer to pollutants as   detected.  This appendix uses the term   quantitated  rather than detected.

B 3 Appendix B  Analytical Methods and Baseline Values follow. EPA proposed limitations or standards based only upon data generated by methods approved in 40 CFR 136. Table B 1 provides a summary of the analytical methods, the associated pollutants measured by the method, the nominal quantitation levels, and the baseline levels. The following sections provide additional information supporting the summary in Table B 1.

The following sections describe the methods used to determine pollutant levels in wastewater samples collected at metal products and machinery facilities. Each section states whether the method is approved at 40 CFR 136 ( even if the pollutant was not proposed to be regulated), provides a short description of the method, identifies the nominal quantitation limit, and explains EPA's choice for the baseline value.

B. 4.1 EPA Methods 1624, 1625, 1664, and OIA 1677 ( Volatile Organics, Semivolatile Organics, HEM, SGT HEM, and Available Cyanide)

EPA used Methods 1624, 1625, 1664, and OIA 1677 to measure volatile organics, semivolatile organics, n hexane extractable material ( HEM)/ silica gel treated n hexane extractable material ( SGT HEM) and available cyanide, respectively. Industry used Method 1664 to measure HEM and SGT HEM. Methods 1624, 1625, 1664, and OIA 1677 are approved at 40 CFR 136.

These methods use the minimum level ( ML) of quantitation. The ML is defined as the lowest level at which the entire analytical system must give a recognizable signal and an acceptable calibration point for the analyte. When an ML is published in a method, the Agency has demonstrated that the ML can be achieved in at least one well operated laboratory. When that laboratory or another laboratory uses that method, the laboratory is required to demonstrate, through calibration of the instrument or analytical system, that it can achieve pollutant measurements at the ML.

For volatile organics, semivolatile organics, HEM/ SGT HEM, and available cyanide, EPA used the method specified MLs as the baseline values. In determining the pollutants of concern and in calculating the HEM/ SGT HEM standards, EPA substituted the value of the ML and assumed that the measurement was not quantitated when a quantitated value or sample specific quantitation limit was reported with a value less than the ML specified in the method. For example, if the ML was 10 g/ L and the laboratory reported a quantitated value of 5 g/ L, EPA assumed that the concentration was nonquantitated with a sample specific quantitation limit of 10 g/ L. The objective of this comparison was to identify any results for the pollutants reported below the method defined ML. Results reported below the ML were changed to the ML to ensure that all results used by EPA were reliable. In most cases, the quantitated values and sample specific quantitation limits were equal to or greater than the baseline values.

B. 4.2 EPA Methods 1620 and 200.7 ( Metals)

EPA used Method 1620 to measure the concentrations of metals. While Method 1620 is not listed at 40 CFR 136 as an approved method, it represents a consolidation of the analytical B 4 Appendix B  Analytical Methods and Baseline Values techniques in several 40 CFR 136 approved methods, such as Method 200.7 ( inductively coupled plasma atomic emission ( ICP) spectroscopy of trace elements) and Method 245.1 ( mercury cold vapor atomic absorption ( CVAA) spectroscopy). This method was developed specifically for the effluent guidelines program. Method 1620 includes more metal analytes than are listed in the approved methods and contains quality control requirements at least as stringent as the 40 CFR 136 approved methods. Some industry supplied results for aluminum, barium, beryllium, cadmium, calcium, chromium, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, sodium, vanadium, and zinc were determined by Method 200.7. Other industry supplied results for metals were determined by EPA Methods 204.1, 206.2, 231.2, 239.1, 245.1, 245.2, 265.2, 270.2, 272.1, 279.1, 7041, 7060A, 7740, and 7841.

Method 1620 employs the concept of an instrument detection limit ( IDL). The IDL is defined as " the smallest signal above background noise that an instrument can detect reliably." 3 Data reporting practices for Method 1620 analyses follow conventional metals reporting practices used in other EPA programs, in which values are required to be reported at or above the IDL. In applying Method 1620, IDLs are determined on a quarterly basis by each analytical laboratory and are, therefore, laboratory specific and time specific. Although Method 1620 contains MLs, these MLs pre date EPA's recent refinements of the ML concept described earlier. The MLs associated with Method 1620 are based on a consensus opinion reached between EPA and laboratories during the 1980s regarding levels that could be considered reliable quantitation limits when using Method 1620. These limits do not reflect advances in technology and instrumentation since the 1980s. Consequently, the IDLs, which are more reflective of current analytical capabilities, were used as the lowest values for reporting purposes, with the general understanding that reliable results can be produced at or above the IDL. Although the baseline values were derived from the MLs ( or adjusted MLs) in Method 1620, EPA used the laboratory reported quantitated values and sample specific quantitation limits, which captured concentrations down to the IDLs, in its data analyses.

In general, EPA used the MLs specified in Method 1620 as the baseline values. However, EPA adjusted the baseline value for lead to 50 : g/ L and boron to 100 : g/ L. In Method 1620, lead has an ML of 5 : g/ L for graphite furnace atomic absorption ( GFAA) spectroscopy analysis; EPA determined, however, that it was not necessary for the laboratories to measure down to such low levels, and that lead could be analyzed by inductively coupled plasma atomic emission ( ICP) spectroscopy. Consequently, the ML requirement was adjusted to 50 : g/ L, the ML for the ICP method. In Method 1620, boron has an ML of 10 : g/ L, but laboratory feedback years ago indicated that laboratories could not reliably achieve this low level. As a result, EPA only required laboratories to measure values at 100 : g/ L and above. Thus, EPA adjusted the baseline value to 100 : g/ L.

3Keith, L. H., W. Crummett, J. Deegan, R. A. Libby, J. K. Taylor, G. Wentler ( 1983).   Principles of Environmental Analysis,  Analytical Chemistry, Volume 55, Page 2217.

B 5 Appendix B  Analytical Methods and Baseline Values B. 4.3 EPA Method 335.1 ( Amenable Cyanide)

Amenable cyanide was measured using Method 335.1, which is approved at 40 CFR 136. Industry also supplied data determined by Method 335.1. Method 335.1 utilizes either a titrimetric or colorimetric procedure to measure amenable cyanide.

Method 335.1 has a lower measurement range limit of 0.02 milligrams per liter ( mg/ L) for the colorimetric procedure and a lower measurement range limit of 1 mg/ L for the titrimetric procedure. The nominal quantitation limit of 0.02 mg/ L was used as the baseline for all amenable cyanide results, since it is the lower value of the two.

B. 4.4 EPA Methods 350.2 and 350.3 ( Ammonia as Nitrogen)

Ammonia, as nitrogen, was measured using Methods 350.2 and 350.3, both of which are approved at 40 CFR 136. Method 350.2 utilizes colorimetric, titrimetric, or electrode procedures to measure ammonia. Method 350.3 uses a potentiometric procedure to measure ammonia.

Method 350.2 has a lower measurement range limit of 0.20 mg/ L for the colorimetric and electrode procedures, and a lower measurement range limit of 1.0 mg/ L for the titrimetric procedure. Method 350.3 has a lower measurement range limit of 0.03 mg/ L for the potentiometric procedure. Rather than use different baseline values for the same pollutant, EPA used 0.03 mg/ L as the baseline value from Method 350.3 because it represents the lowest value at which ammonia as nitrogen can be measured reliably.

B. 4.5 EPA Method 405.1 and SM 5210B ( BOD5 and Carbonaceous BOD5 )

Biochemical oxygen demand ( BOD5 ) and carbonaceous BOD5 ( cBOD5 ) were measured using Method 405.1 and Standard Method ( SM) 5210B, both of which are approved at 40 CFR 136. BOD5 and cBOD5 are determined by the same method, except that an organic compound is added to the cBOD5 test to inhibit nitrogenous oxygen demand. If the sample does not include any nitrogenous demand to inhibit, the results should be comparable for BOD5 and cBOD5 .

Method 405.1 and SM 5210B are identical and the nominal quantitation limit, which is expressed in the methods as the lower limit of the measurement range at 2 mg/ L, is the same for both forms of BOD5 . EPA used this nominal quantitation limit of 2 mg/ L as the baseline value in determining the pollutants of concern.

B. 4.6 EPA Methods 410.1, 410.2, and 410.4 ( Chemical Oxygen Demand)

Chemical Oxygen Demand ( COD) was measured using Methods 410.1, 410.2, and 410.4, all of which are approved at 40 CFR 136. Method 410.4 is a colorimetric procedure. Methods 410.1 and 410.2 are titrimetric procedures that follow identical analytical protocols; they B 6 Appendix B  Analytical Methods and Baseline Values differ only in the range of COD concentration that they are designed to measure. Reagent concentrations and sample volumes are adjusted to accommodate a wide range of sample concentrations, since the dynamic range of the chemistry used to detect COD is somewhat limited. Data from all three of these methods are directly comparable.

Method 410.1 is designed to measure mid level concentrations ( greater than 50 mg/ L) of COD and is associated with a nominal quantitation limit of 50 mg/ L. Method 410.2 is designed to measure low level concentrations in the range of 5 50 mg/ L. Method 410.4 has a measurement range of 3 900 mg/ L for automated procedures and measurement range of 20 900 mg/ L for manual procedures. EPA contracts required that laboratories measure down to the lowest quantitation limit possible for whatever method is used. Therefore, if the laboratory analyzes a sample using Method 410.1 and obtains a nonquantitated result, it must reanalyze the sample using Method 410.2. Thus, the quantitation limit reported for nonquantitated was 5 mg/ L, unless sample dilutions were required for complex matrices.

For all COD data, EPA used the baseline value of 5 mg/ L that is associated with the lower quantitation limit for the titrimetric procedures because most of the data used to determine COD were obtained by the titrimetric procedures ( i. e., Methods 410.1 and 410.2).

B. 4.7 EPA Method 325.3 ( Chloride)

Chloride was measured using Method 325.3, which is approved at 40 CFR 136. Method 325.3 is a titrimetric procedure and measures concentrations greater than 1 mg/ L; therefore, EPA used the baseline value of 1 mg/ L.

B. 4.8 EPA Method 340.2 ( Fluoride)

Fluoride was determined by Method 340.2, which is approved at 40 CFR 136. Method 340.2 is a potentiometric procedure that uses a fluoride electrode. The nominal quantitation limit of 0.1 mg/ L is expressed in the method as the lower limit of the measurement range. This nominal quantitation limit was used as the baseline value for fluoride.

B. 4.9 EPA Method 218.4, SM 3111A, and SM 3500D ( Hexavalent Chromium)

For EPA sampling episodes, hexavalent chromium was determined by Method 218.4 and SM 3500D, which are approved at 40 CFR 136. Industry supplied data generated by SM 3111A which is not approved at 40 CFR 136. Method 218.4 utilizes atomic absorption for the determination of hexavalent chromium after chelation and extraction. SM 3500D is a colorimetric procedure using reaction with diphenylcarbazide to produce a color proportional to Cr6+ concentration. SM 3111A utilizes flame atomic absorption spectrometry to measure Cr6+ or total Cr.

B 7 Appendix B  Analytical Methods and Baseline Values In Method 218.4, SM 3111A, and SM 3500D, the nominal quantitation limit or lower limit of the measurement range is 0.01 mg/ L. Because EPA used Methods 218.4 and SM 3500D for analysis, the nominal quantitation limit of 0.01 mg/ L was used as the baseline value for all hexavalent chromium results.

B. 4.10 EPA Method 150.1 and SM 4500H ( pH)

For EPA sampling episodes, pH was determined by Method 150.1. For industry supplied data, pH was determined by SM 4500H. Both methods are approved at 40 CFR 136. For Method 150.1 and SM 4500H, the pH of a sample is determined electrometrically using either a glass electrode in combination with a reference potential or a combination electrode. There are no nominal quantitation limits for either Method 150.1 or SM 4500H.

B. 4.11 EPA Methods 375.2 and 375.4 ( Sulfate)

For EPA sampling episodes, sulfate was measured by Methods 375.2 and 375.4. For industry supplied data, sulfate was measured by Method 375.4. Both of these methods are approved at 40 CFR 136. Method 375.2 is a colorimetric procedure that uses the decrease in color caused by the formation of barium sulfate to measure the sulfate concentration. Method 375.4 measures the turbidity created by the insoluble barium sulfate in solution. A dispersant/ buffer is added to the solution to aid in creating uniform suspension of the barium sulfate.

The nominal quantitation limit ( also the lower limit of the measurement range) for Method 375.2 is 0.50 mg/ L. The nominal quantitation limit ( also the lower limit of the measurement range) for Method 375.4 is 1 mg/ L. EPA used the baseline value of 1 mg/ L that is associated with the higher quantitation limit for all the sulfate data, rather than having multiple baseline values, because most of the sulfate data was determined by Method 375.4.

B. 4.12 EPA Methods 335.2 and 335.3 ( Total Cyanide)

EPA determined total cyanide using Method 335.2. Industry determined total cyanide by Methods 335.2 and 335.3. Both methods are approved at 40 CFR 136. Method 335.2 uses either titration with silver nitrate, or colorimetry with an organic dye, to measure total cyanide. Method 335.3 uses an automated distillation colorimetry procedure for continuous flow analytical systems that utilizes UV oxidation to measure total cyanide.

The nominal quantitation limit for Method 335.2, expressed in the method as the lower limit of the measurement range, is 0.02 mg/ L. The nominal quantitation limit for Method 335.3, also expressed as the lower limit of the measurement range, is 0.005 mg/ L. Because EPA used Method 335.2, the Agency used the nominal quantitation limit of 0.02 mg/ L as the baseline value for all total cyanide results.

B 8 Appendix B  Analytical Methods and Baseline Values B. 4.13 EPA Method 160.1 and SM 2540C ( Total Dissolved Solids)

EPA determined total dissolved solids ( TDS) by Method 160.1. Industry determined TDS by SM 2540C. Both methods are approved at 40 CFR 136 under " residue filterable." Method 160.1 and SM 2540C are gravimetric methods with a lower limit of the measurement range of 10 mg/ L; this value is the nominal quantitation limit. The nominal quantitation limit of 10 mg/ L is also the baseline value.

B. 4.14 EPA Method 351.3 ( Total Kjeldahl Nitrogen)

EPA determined total Kjeldahl nitrogen ( TKN) by Method 351.3, which is approved at 40 CFR 136. Method 351.3 is a manual colorimetric analysis that has a lower measurement range limit, which is also the nominal quantitation limit, of 1.0 mg/ L. The nominal quantitation limit of 1.0 mg/ L is also the baseline value.

B. 4.15 EPA Method 415.1 ( Total Organic Carbon)

EPA determined total organic carbon ( TOC) by Method 415.1, which is approved at 40 CFR 136. Method 415.1 is a combustion ( or oxidation) method with a lower measurement range limit of 1 mg/ L. EPA used this nominal quantitation limit of 1 mg/ L as the baseline value.

B. 4.16 EPA Methods 420.1 and 420.2 ( Total Phenols)

In EPA's database, the terms " total phenols" and " total recoverable phenolics" are used synonymously. The term " total recoverable phenolics" is used in the titles of Methods 420.1 to 420.4. While " total recoverable phenolics" could be considered a more accurate term for what is measured in any of these related methods, both terms refer to an aggregate measure of compounds with a phenol like or " phenolic" structure. The use of the adjective " recoverable" simply recognizes that there are some compounds that are not measured, as well as other related compounds in this class. Thus, the method reports what can be recovered from the sample under the conditions of the analysis.

The methods for the analysis of total phenols employ the reagent 4 aminoantipyrine ( 4AAP), which reacts with phenolic compounds to produce a dark red product, an antipyrine dye. The concentration of the phenolic compounds is determined by measuring the absorbance of the sample at a wavelength of 460 to 520 nm, depending on the method. The methods are calibrated using a series of standards containing the single compound phenol. Methods 420.1 and 420.2, the two methods approved at 40 CFR 136, provide several options for sample preparation and analysis, including a preliminary distillation designed to remove interferences, and a chloroform extraction procedure in Method 420.1 that is designed to improve the sensitivity of the method. Both methods also provide information on the concentrations of the calibration standards that may be prepared for a given set of procedural options.

B 9 Appendix B  Analytical Methods and Baseline Values The methods themselves do not contain a required calibration range. Each laboratory can, and does, establish a calibration range based on its use of the method. EPA used a baseline value of 0.05 mg/ L because this was the most commonly reported sample specific detection limit in EPA's sampling episode data ( these data included more concentrated samples than effluent).

B. 4.17 EPA Methods 365.2 and 365.3 ( Total Phosphorus)

EPA determined total phosphorus by Methods 365.2 and 365.3. Both methods are approved at 40 CFR 136. Total phosphorus represents all of the phosphorus present in the sample, regardless of form, as measured by the persulfate digestion procedure.

The two methods differ only in the preparation of one of the reagents. Method 365.2 specifies the separation of the ammonium molybdate and the antimony potassium tartrate from the ascorbic acid reagent. Method 365.3 allows for combining these reagents into a single solution. Because the chemistry is unaffected, the data are directly comparable.

These methods have the same nominal quantitation limit of 0.01 mg/ L. EPA used this value as the baseline value for total phosphorus.

B. 4.18 EPA Methods 376.1 and 376.2, SM 4500D and SM 4500E, and D4658 ( Total Sulfide)

EPA determined total sulfide by Methods 376.1, 376.2, and SM 4500E, all of which are approved at 40 CFR 136. Industry determined sulfide by SM 4500D and ASTM Method D4658. SM 4500D is approved at 40 CFR 136, while ASTM Method D4658 is not approved at 40 CFR 136. Method 376.1 and SM 4500E utilize an iodine solution to oxidize any sulfide present in the sample. The remaining iodine is then titrated with sodium thiosulfate in the presence of a starch solution. The quantity of iodine added to the sample and the titrant required to neutralize the remaining iodine give the sulfide concentration by calculation. Method 376.2 and SM 4500D use the reaction of the sulfide ion with ferric chloride and dimethyl P phenylenediamine to produce deeply colored methylene blue. The color is proportional to the sulfide concentration. ASTM Method D4658 utilizes an ion selective electrode to determine sulfide ion in water.

EPA collected sulfide data for 236 samples in seven post proposal sampling episodes using Methods 376.1, 376.2, and SM 4500E ( EPA Episode numbers 6455, 6456, 6457, 6458, 6461, 6462, and 6463). These samples were collected from both process wastewaters prior to treatment and effluent wastewater after treatment. EPA reviewed the analytical data from these 236 samples and compared the three different methods. The study is included in the rulemaking record ( see Section 16.2 of the rulemaking record, DCN 16941) and a summary of the findings are in the notice of data availability ( 67 FR 38754; June 5, 2002).

B 10 Appendix B  Analytical Methods and Baseline Values The nominal quantitation limit for Method 376.1 and SM 4500E, which is also the lower limit of the measurement range, is 1.0 mg/ L. The nominal quantitation limit for Method 376.2 and SM 4500D is 0.5 mg/ L. The nominal quantitation limit for D4658, which is also the lower limit of the measurement range, is 0.04 mg/ L. Rather than use different baseline values for the same pollutant, EPA used the 1.0 mg/ L as the baseline value from Method 376.1 because the majority of the data were determined by this method.

B. 4.19 EPA Method 160.2 and SM 2540D ( Total Suspended Solids)

EPA determined total suspended solids ( TSS) by Method 160.2. Industry determined TSS by SM 2540D. Both methods are approved at 40 CFR 136 under " residue non filterable." Method 160.2 and SM 2540D are gravimetric methods with a lower limit of the measurement range of 4 mg/ L; this value is also the nominal quantitation limit. The nominal quantitation limit of 4 mg/ L is the baseline value.

B. 4.20 EPA Method 204.1 and 7041 ( Antimony)

Industry determined antimony by Methods 204.1 and 7041. Method 204.1 is approved at 40 CFR 136. Method 7041 is from Test Methods for Evaluating Solid Waste, Physical/ Chemical Methods ( SW 846). Although Method 7041 is not listed at 40 CFR 136, it is approved for analyses of samples under the RCRA regulations at 40 CFR 261. Method 204.1 utilizes direct aspiration atomic absorption as the determinative technique to measure antimony. Method 7041 utilizes the furnace technique in conjunction with an atomic absorption spectrophotometer.

The nominal quantitation limit ( also the lower limit of the measurement range) for Method 204.1 is 1.0 mg/ L. The nominal quantitation limit ( also the lower limit of the measurement range) for Method 7041 is 20 : g/ L. Rather than use different baseline values for the same pollutant, EPA used the minimum level of 20 : g/ L for antimony from Method 1620 as the baseline value, because this was the method that EPA used for the determination of antimony.

B. 4.21 EPA Method 206.2 and 7060A ( Arsenic)

Industry determined arsenic by Methods 206.2 and 7060A. Method 206.2 is approved at 40 CFR 136. Method 7060A is from Test Methods for Evaluating Solid Waste, Physical/ Chemical Methods ( SW 846). Although Method 7060A is not listed at 40 CFR 136, it is approved for analyses of samples under the RCRA regulations at 40 CFR 261. Methods 206.2 and 7060A utilize the furnace technique in conjunction with an atomic absorption spectrophotometer.

The nominal quantitation limit ( also the lower limit of the measurement range) for Method 206.2 and Method 7060A is 5.0 : g/ L. Rather than use different baseline values for the same pollutant, EPA used the minimum level of 10 : g/ L for arsenic from Method 1620 as the baseline value, because this was the method that EPA used for the determination of arsenic.

B 11 Appendix B  Analytical Methods and Baseline Values B. 4.22 EPA Method 231.2 ( Gold)

EPA determined gold by Method 231.2, since this parameter is only semiquantitatively analyzed by Method 1620. Method 231.2 is approved at 40 CFR 136. Method 231.2 utilizes the furnace technique in conjunction with an atomic absorption spectrophotometer. The nominal quantitation limit for gold, which is also the lower limit of the measurement range, is 5 : g/ L. The nominal quantitation limit is also the baseline value.

B. 4.23 EPA Method 239.1 ( Lead)

Industry determined lead by Method 239.1, which is approved at 40 CFR 136. Method 239.1 utilizes direct aspiration atomic absorption as the determinative technique to measure lead. The nominal quantitation limit of 0.1 mg/ L is expressed in the method as the lower limit of the measurement range. Rather than use different baseline values for the same pollutant, EPA used the minimum level of 50 : g/ L for lead from Method 1620 from the ICP technique, as the baseline value since this was the method that EPA used for the determination of lead.

B. 4.24 EPA Methods 245.1 and 245.2 ( Mercury)

Industry determined mercury by Methods 245.1 and 245.2, both of which are approved at 40 CFR 136. The methods utilize cold vapor atomic absorption as the determinative technique to measure mercury. The nominal quantitation limit for both methods is 0.2 : g/ L, which is also expressed as the lower limit of the measurement range. The nominal quantitation limit matches the nominal quantitation limit from Method 1620, which EPA used to determine mercury. The nominal quantitation limit is the same as the baseline value of 0.2 : g/ L.

B. 4.25 EPA Method 265.2 ( Rhodium)

EPA determined rhodium by Method 265.2, since this parameter is only semiquantitatively analyzed by Method 1620. Method 265.2 is approved at 40 CFR 136. Method 265.2 utilizes the furnace technique in conjunction with an atomic absorption spectrophotometer. The nominal quantitation limit for rhodium, which is also the lower limit of the measurement range, is 20 : g/ L. The nominal quantitation limit is also the baseline value.

B. 4.26 EPA Methods 270.2 and 7740 ( Selenium)

Industry determined selenium by Methods 270.2 and 7740. Method 270.2 is approved at 40 CFR 136. Method 7740 is from Test Methods for Evaluating Solid Waste, Physical/ Chemical Methods ( SW 846). Although Method 7740 is not listed at 40 CFR 136, it is approved for analyses of samples under the RCRA regulations at 40 CFR 261. Methods 270.2 and 7740 utilize the furnace technique in conjunction with an atomic absorption spectrophotometer.

B 12 Appendix B  Analytical Methods and Baseline Values The nominal quantitation limit for Method 270.2 and Method 7740, which is also lower limit of the measurement range, is 5.0 : g/ L. Rather than use different baseline values for the same pollutant, EPA used the minimum level of 5 : g/ L for selenium from Method 1620 as the baseline value, since this was the method that EPA used for the determination of selenium.

B. 4.27 EPA Method 272.1 ( Silver)

Industry determined silver by Method 272.1, which is approved at 40 CFR 136. Method 272.1 utilizes direct aspiration atomic absorption as the determinative technique to measure silver. The nominal quantitation limit of 0.1 mg/ L is expressed in the method as the lower limit of the measurement range. Rather than use different baseline values for the same pollutant, EPA used the minimum level of 10 : g/ L for silver from Method 1620 as the baseline value, since this was the method that EPA used for the determination of silver.

B. 4.28 EPA Methods 279.1 and 7841 ( Thallium)

Industry determined thallium by Methods 279.1 and 7841. Method 279.1 is approved at 40 CFR 136. Method 7841 is from Test Methods for Evaluating Solid Waste, Physical/ Chemical Methods ( SW 846). Although Method 7841 is not listed at 40 CFR 136, it is approved for analyses of samples under the RCRA regulations at 40 CFR 261. Method 279.1 utilizes direct aspiration atomic absorption as the determinative technique to measure thallium. Method 7841 utilizes the furnace technique in conjunction with an atomic absorption spectrophotometer.

The nominal quantitation limit for Method 279.1, which is also the lower limit of the measurement range, is 1.0 mg/ L. The nominal quantitation limit for Method 7841, which is also the lower limit of the measurement range, is 5 : g/ L. Rather than use different baseline values for the same pollutant, EPA used the minimum level of 10 : g/ L for thallium from Method 1620 as the baseline value, since this was the method that EPA used for the determination of thallium.

B. 4.29 EPA Methods 624 and 625 ( Volatile Organics and Semivolatile Organics)

EPA included industry supplied data from Methods 624 and 625, both of which are approved at 40 CFR 136. Methods 624 and 625 are GC/ MS methods, similar to Methods 1624 and 1625, except that Methods 624 and 625 do not utilize isotope dilution. The nominal quantitation limits are expressed as the lower limit of the measurement range, typically the concentration of the lowest calibration standard. However, rather than use different baseline values for the same pollutants ( Methods 624 and 625 have many of the same analytes as Methods 1624 and 1625), EPA used the minimum levels that are listed in Methods 1624 and 1625 as the baseline values, since these methods were used by EPA for the determination of volatile and semivolatile organic analytes.

B 13 Appendix B  Analytical Methods and Baseline Values B. 4.30 EPA Method 630.1 ( Ziram)

Ziram was determined by Method 630.1. There are no methods approved at 40 CFR 136 for ziram. In this method, the sample is digested with acid to yield CS2 by hydrolysis of the dithiocarbamate moiety. The evolved CS2 is extracted from the water with hexane and the extract is injected into a GC. The nominal quantitation limit was determined by a low point calibration standard. The nominal quantitation limit for ziram is 10 : g/ L and was used as the baseline value.

Analytical Method Development Efforts Section 304( h) of the Clean Water Act directs EPA to promulgate guidelines establishing test procedures for the analysis of pollutants. These methods allow the analyst to determine the presence and concentration of pollutants in wastewater. The methods are used for compliance monitoring, for filing applications for the NPDES program under 40 CFR 122.21, 122.41, 122.44 and 123.25, and for the implementation of the pretreatment standards under 40 CFR 403.10 and 403.12. To date, EPA has promulgated methods for all conventional and toxic pollutants, and for some nonconventional pollutants.

Currently approved methods for metals and wet chemistry parameters are included in the table of approved inorganic test procedures at 40 CFR 136.3, Table I B. Table I C at 40 CFR 136.3 lists approved methods for measurement of nonpesticide organic pollutants, and Table I D lists approved methods for the toxic pesticide pollutants and for other pesticide pollutants. Dischargers must use the test methods promulgated at 40 CFR 136.3 or incorporated by reference in the tables, when available, to monitor pollutant discharges from the metal products and machinery ( MP& M) industry, unless specified otherwise in 40 CFR 413, 433, 438, 463, 464, 467, and 471, or by the permitting authority.

Table I C does not include six of the MP& M semivolatile organic pollutants and one of the MP& M volatile organic pollutant that EPA is regulating in the rule. Although these pollutants are missing from Table I C, the analyte list for Method 1624 contains the volatile organic pollutant and the analyte list for Method 1625 contains the six semivolatile organic pollutants. EPA promulgated both of these methods for use in Clean Water Act measurement programs at 40 CFR 136, Appendix A.

As a part of the rule, EPA will allow the use of modified versions of Methods 624 and 1624 for the determination of the additional volatile organic pollutant and modified versions of Methods 625 and 1625 for the determination of the additional six semivolatile organic pollutants.

The modifications to Methods 624, 625, 1624, and 1625 have been included in the Docket for the rule. The modifications to Methods 624, 625, 1624, and 1625 consist of text, performance data, and quality control ( QC) acceptance criteria for the additional analytes. This information will allow a laboratory to practice the methods with the additional analytes as an integral part. EPA conducted an interlaboratory validation study on the modifications to these methods. The B 14 B. 5 Appendix B  Analytical Methods and Baseline Values data from the interlaboratory study and the proposed modifications to the method were made available for public comment in a notice of data availability ( see Section B. 4.18). EPA is promulgating these method modifications for monitoring MP& M industry wastewaters at 40 CFR 136 in the rule.

As part of the rule, the following pollutants will be added to their respective analyte lists for the MP& M industry only:

Methods Pollutant CAS Number EPA Methods 624/ 1624 carbon disulfide 75 15 0 EPA Methods 625/ 1625 aniline 62 53 3 EPA Methods 625/ 1625 3,6 dimethylphenanthrene 1576 67 6 EPA Methods 625/ 1625 2 isopropylnaphthalene 2027 17 0 EPA Methods 625/ 1625 1 methylfluorene 1730 37 6 EPA Methods 625/ 1625 2 methylnaphthalene 91 57 6 EPA Methods 625/ 1625 1 methylphenanthrene 832 69 9 B 15 Appendix B  Analytical Methods and Baseline Values Table B 1 Analytical Methods and Baseline Values Analyte Method CAS Number Samples Collected and Analyzed by Nominal Quantitation Value ( mg/ L) Baseline Value ( mg/ L)

Amenable Cyanide 335.1 C025 EPA, Industry 0.02 0.02 Ammonia as Nitrogen 350.2 766417 EPA 0.05 0.05 350.3 0.03 Available Cyanide OIA 1677 C054 EPA 0.002 0.002 BOD Carbonaceous BOD 405.1 C003 EPA 2.00 2.00 5210B C002 2.00 Chemical Oxygen Demand 410.1 C004 EPA 50.00 5.00a 410.2 5.00 410.4( automated) b 3.00 410.4( manual) b 20.00 Chloride 325.3 16887006 EPA 1.00 1.00 Fluoride 340.2 16984488 EPA 0.10 0.10 HEM, SGT HEM 1664 C036, C037 EPA, Industry 5.00 5.00 Hexavalent Chromium 218.4 18540299 EPA 0.01 0.01 3111A Industry 0.01 3500D EPA 0.01 Metals 1620 c EPA c c 200.7 c Industry c c pH 150.1 C006 EPA N/ A 4500H Industry N/ A Semivolatile Organics 1625 c EPA c c 625 Industry Sulfate 375.2 14808798 EPA 3.00 1.00 375.4 EPA, Industry 1.00 Total Cyanide 335.2 57125 EPA, Industry 0.02 0.02 335.3 Industry 0.005 TDS 160.1 C010 EPA 10.00 10.00 2540C Industry 10.00 TKN 351.3 C021 EPA 1.00 1.00 TOC 415.1 C012 EPA 1.00 1.00 Total Phenols 420.1 C020 EPA d 0.05 420.2 d Total Phosphorus 365.2 14265442 EPA 0.01 0.01 365.3 0.01 B 16 Appendix B  Analytical Methods and Baseline Values Table B 1 ( Continued)

Analyte Method CAS Number Samples Collected and Analyzed by Nominal Quantitation Value ( mg/ L) Baseline Value ( mg/ L)

Total Sulfide 376.1 18496258 EPA 1.00 1.00 376.2 0.10 4500D Industry 0.50 4500E EPA 1.00 D4568 Industry 0.04 TSS 160.2 C009 EPA 4.00 4.00 2540D Industry 4.00 Volatile Organics 1624 c EPA c c 624 Industry Ziram 630.1 137304 EPA 0.01 0.01 aThe baseline value was adjusted to reflect the lowest nominal quantitation limit of the titrimetric procedures ( i. e., 410.1, 410.2, and 5220B). See Section B. 4.6 for a detailed explanation. bMethod 410.4 lists two different quantitation limits that are dependent upon whether the automated or manual protocols were followed. The automated method limit = 3 mg/ L and the manual method limit = 20 mg/ L. cThe method analyzed a number of pollutants each with its own CAS number, baseline value, and nominal quantitation limit. dThe method does not have a required calibration range. The baseline value is based upon the most frequently reported sample specific detection limit.

B 17 Appendix C  Wastewater Characteristics Appendix C WASTEWATER CHARACTERISTICS Appendix C  Wastewater Characteristics Appendix C WASTEWATER CHARACTERISTICS This appendix summarizes the characteristics of wastewater generated by unit operations evaluated for the final rule and discharged to wastewater treatment systems. The wastewaters characterized in this appendix can be grouped into the following types of wastewaters:

C Hexavalent chromium bearing wastewater; C Cyanide bearing wastewater; C Oil bearing and organic pollutant bearing wastewaters; C Chelated metal bearing wastewater; and C Metal bearing wastewater.

EPA evaluated a number of unit operations for the May 1995 proposal, January 2001 proposal, and June 2002 NODA ( see Tables 4 3 and 4 4). However, EPA selected a subset of these unit operations for regulation in the final rule ( see Section 1.0). For this appendix, the term " proposed MP& M operations" means those operations evaluated for the two proposals, NODA, and final rule. The term " final MP& M operations" means those operations defined as " oily operations" ( see Section 1.0, 40 CFR 438.2( f), and Appendix B to Part 438) and regulated by the final rule.

Sections C. 1 through C. 5 summarize, for each type of wastewater, analytical data obtained during the MP& M regulatory development process for unit operations and influents to the wastewater treatment systems. These subsections present the number of samples analyzed, the number of times each pollutant was detected, and the minimum, maximum, mean, and median pollutant concentrations. Oil bearing and organic pollutant bearing wastewaters are characterized in Section 5.0.

Analytical data from the MP& M sampling program, including data obtained from sanitation districts, facilities performing proposed MP& M operations, and MP& M industry trade associations, are in the sampling episode reports located in Sections 5.2 and 15.3 of the rulemaking record.

C. 1 Hexavalent Chromium Bearing Wastewater Hexavalent chromium bearing wastewater exhibits high concentrations of hexavalent chromium and may contain other metals, and generally has a low pH of approximately 2. Sections C. 1.1 and C. 1.2 present chromium data for process water and associated rinse water and for the influent to the chromium reduction process, respectively.

C 1 Appendix C  Wastewater Characteristics C. 1.1 Process Water and Rinse Water Hexavalent chromium is present in process bath wastewater from various unit operations ( e. g., chromic acid anodizing, chromate conversion coating, and chromium electroplating). Table C 1 presents the number of samples collected and analyzed during EPA s sampling program for unit operations and associated rinses that generate hexavalent chromium bearing wastewater.

Table C 1 Number of Process and Rinse Water Samples for Unit Operations That Generate Hexavalent Chromium Bearing Wastewater Unit Operation No. of Process Water Samples No. of Rinse Water Samples Acid Treatment with Chromium Anodizing with Chromium Chromate Conversion Coating ( Or Chromating)

Electroplating with Chromium Wet Air Pollution Control 1 2 16 4 6 3 7 23 10 NA Source: MP& M Sampling Program. NA  Not applicable. No associated rinse.

The mean total and hexavalent chromium concentrations in process bath water from these operations are 24,120 milligrams per liter ( mg/ L) and 10.0 mg/ L, respectively. In the associated rinses, the mean concentrations for total and hexavalent chromium are 156 mg/ L and 10.3 mg/ L, respectively. Table C 2 summarizes total and hexavalent chromium concentration data for the process bath water and rinse water samples with detected concentrations for the unit operations listed in Table C 1.

Table C 2 Chromium Concentration Data for Process Water and Rinse Water Source Chromium Form No. of Samples Analyzed No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Process Water Total 29 29 0.045 139,000 24,120 2,990 Hexavalent 2 1 10.0 10.0 10.0 10.0 Rinse Water Total 43 43 0.22 1,762 156 12.8 Hexavalent 6 6 2.1 21.2 10.3 8.0 Source: MP& M Sampling Program.

C 2 Appendix C  Wastewater Characteristics C. 1.2 Influent to Chromium Reduction Process Facilities performing proposed MP& M operations usually segregate hexavalent chromium bearing wastewater and treat it in a chromium reduction unit before commingling it with other process wastewater for further treatment. This segregated wastewater requires preliminary treatment to reduce hexavalent chromium to trivalent chromium because the chemical precipitation systems typically used to treat the commingled wastewater do not effectively treat hexavalent chromium. Typical chrome treatment involves chromium reduction using sulfur dioxide, sodium bisulfite, sodium metabisulfite, peroxide, or ferrous sulfate ( see Section 8.4.1). Table C 3 presents the total and hexavalent chromium concentration data for samples of the influent to the chromium reduction process collected during EPA s sampling program. The treatment influent typically represents several commingled wastestreams, most of which are rinses. The influent to treatment concentrations are typically lower than the concentrations of process and rinse water due to the number of high flow, low concentration rinses that are commingled prior to treatment.

Table C 3 Chromium Concentration Data for the Influent to the Chromium Reduction Process Form of Chromium No. of Samples Analyzed No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Total Chromium 54 54 0.2 432 54.8 18.2 Hexavalent Chromium 21 18 0.027 20 6.7 4.0 Source: MP& M Sampling Program.

Cyanide Bearing Wastewater Cyanide bearing wastewater exhibits high concentrations of cyanide and metals such as copper, cadmium, and zinc, and generally has a high pH of approximately 12. Electroplating baths usually are the source of the high concentrations of cyanide. Cyanide may be analyzed as total cyanide ( i. e., all forms included), amenable cyanide ( i. e., cyanide present in forms amenable to treatment using alkaline chlorination), or weak acid dissociable cyanide ( i. e., cyanide that dissociates in a weak acid). Sections C. 2.1 and C. 2.2 present cyanide concentration data for cyanide bearing wastewater generated in proposed MP& M operations and in the influent to the cyanide treatment processes, respectively.

C 3 C. 2 Appendix C  Wastewater Characteristics C. 2.1 Process Water and Rinse Water Table C 4 presents the number of process and rinse water samples collected and analyzed during EPA s sampling program for proposed MP& M operations that generate cyanide bearing wastewater.

Table C 4 Number of Process and Rinse Water Samples for Unit Operations That Generate Cyanide Bearing Wastewater Unit Operation No. of Process Water Samples No. of Rinse Water Samples Alkaline Treatment with Cyanide Electroplating with Cyanide Wet Air Pollution Control 2 11a 3 4 13 NA Source: MP& M Surveys and MP& M Site Visits. a Does not include one sample from a gold cyanide electroplating bath that was analyzed only for metals. NA  Not applicable. No associated rinse.

Cyanide is used as a complexing agent in electroplating and cleaning baths and is present in wastewater generated in the wet air pollution control systems. Table C 5 summarizes the total and amendable cyanide concentration data for the process water and rinse water samples with detected concentrations for the unit operations listed in Table C 4.

Table C 5 Cyanide Concentration Data for Process Water and Rinse Water Source Cyanide Form No. of Samples Analyzed No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Process Water Total 15 15 2.6 100,000 16,521 5,200 Amenable 1 0 NA NA NA NA Rinse Water Total 17 17 0.054 135 38 12.7 Amenable 3 3 61.5 135 100 104 Source: MP& M Sampling Program. NA  Not applicable. No samples were analyzed for amenable cyanide.

C 4 Appendix C  Wastewater Characteristics C. 2.1 Influent to Cyanide Treatment Process Facilities performing proposed MP& M operations usually segregate cyanide bearing wastewater generated and treat it in a cyanide reduction process before commingling it with other process wastewater for further treatment. This preliminary treatment prevents cyanide complexes from forming in the commingled wastewater. Typical cyanide treatment methods include alkaline chlorination with sodium hypochlorite or chlorine gas or ozone oxidation ( see Section 8.4.3). These complexes decrease the effectiveness of chemical precipitation, the technology typically used to treat the commingled wastewater. Table C 6 summarizes the cyanide concentration data for the influent to cyanide treatment process. The treatment influent typically represents several commingled wastestreams, most of which are rinses. The influent to treatment concentrations are typically lower than the concentrations of process and rinse water due to the number of high flow, low concentration rinses that are commingled prior to treatment.

Table C 6 Cyanide Concentration Data for Influent to the Cyanide Treatment Process Form of Cyanide No. of Samples Analyzed No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Total Cyanide 101 98 0.024 1,110 50.7 6.1 Amenable Cyanide 70 65 0.01 394 34.4 3.15 Source: MP& M Sampling Program.

C. 3 Oil Bearing and Organic Pollutant Bearing Wastewaters Oil bearing wastewater exhibits high concentrations of oil and concentrations of organic pollutants. Oil bearing wastewater is classified as containing either free ( floating) oils or oil/ water emulsions. As previously discussed above,   oily operations  are defined and regulated in the final rule and described in Section 4.0. The wastewater from oily operations is characterized in Section 5.0. In addition, EPA collected data on two proposed MP& M operations ( Bilge Water and Dry Dock) that also generate oil bearing and organic pollutant bearing wastewaters. EPA is not regulating these two operations as EPA excluded the proposed Shipbuilding Dry Dock Subcategory from the final rule ( see Section 9.0). Sampling episode reports for the proposed Shipbuilding Dry Dock Subcategory are located in Sections 5.2 and 15.2 of the rulemaking record.

C. 4 Chelated Metal Bearing Wastewater Chelated metal bearing wastewater exhibits high concentrations of metals, usually copper or nickel. Section C. 4.1 discusses the various unit processes that generate chelated metal

C 5 Appendix C  Wastewater Characteristics bearing wastewater and presents process water and rinse water pollutant concentration data for those processes collected during EPA s sampling program. Section C. 4.2 discusses the pollutant concentration data for the influent to chelation breaking preliminary treatment systems.

C. 4.1 Process Water and Rinse Water Facilities performing proposed MP& M operations use chelating agents in unit operations to prevent metals from being precipitated in the process bath. Electroless plating processes and associated rinses are the most common proposed MP& M operations that generate chelated metal bearing wastewater. Some cleaning operations also generate chelated metal bearing wastewater.

To characterize process waters and associated rinse waters for proposed MP& M operations that use chelating agents, EPA collected 37 samples of electroless plating solutions and rinses from electroless nickel plating, or from electroless copper. The maximum concentration of nickel in the process water and the rinses was 7,530 mg/ L and 378 mg/ L, respectively. The maximum concentration of copper in the process water and the rinses was 14,200 mg/ L and 138 mg/ L, respectively. Only one sample of tin was taken from process water, which had a concentration of 3.8 mg/ L. Other metals typically plated using electroless plating include gold, palladium, and cobalt.

C. 4.2 Influent to Chelate Breaking Preliminary Treatment System Typical chemical precipitation and sedimentation treatment processes do not remove chelated metals; therefore, facilities performing proposed MP& M operations usually segregate and pretreat chelated metal bearing wastewater to break down the metal chelates before commingling it with other metal bearing wastewaters. Preliminary treatment may consist of chemical reduction using reducing agents such as sodium borohydride, hydrazine, dithiocarbamate ( measured analytically as ziram) or sodium hydrosulfite; high pH precipitation using calcium hydroxide or ferrous sulfate; or filtering the chelated metals out of solution ( see Section 8.4.4).

EPA measured copper in concentrations ranging from 570 to 700 mg/ L in the influent to the preliminary treatment systems for electroless copper processes. EPA measured nickel in concentrations ranging from 0.149 to 480 mg/ L in the influent to the preliminary treatment systems for electroless nickel processes. Copper and nickel electroless plating are the most prevalent electroless plating operations seen at facilities performing proposed MP& M operations.

C. 5 Metal Bearing Wastewater All of the wastewaters generated in proposed MP& M operations can contain metals, including the wastewaters described in the previous subsections. Section C. 5.1 discusses proposed MP& M operations not presented in the previous subsections that generate metal bearing wastewater and presents pollutant concentration data for the process water and rinse water for those operations.

C 6 Appendix C  Wastewater Characteristics Section C. 5.2 presents pollutant concentration data for the influent to chemical precipitation systems used to treat metal bearing wastewater.

C. 5.1 Process Water and Rinse Water Table C 7 lists the proposed MP& M operations that generate metal bearing wastewater and presents the number of samples of process water and rinse water collected and analyzed in EPA s sampling program for each unit operation.

Facilities performing proposed MP& M operations typically use metals in the process baths for unit operations such as electroplating and stripping. Tables C 8 and C 9 summarize the pollutant concentration data for process water and rinse water, respectively, collected during the MP& M sampling program for unit operations generating metal bearing wastewater. As shown in the tables, the metal priority pollutants most frequently detected in samples of process water were copper, zinc, chromium, nickel, and lead. Nonconventional metal pollutants frequently detected include iron, magnesium, boron, barium, manganese, and aluminum. The process water and rinses also typically contained oil and grease, total suspended solids, and low concentrations of organic pollutants.

C. 5.2 Influent to the Chemical Precipitation Treatment Systems Typically, facilities performing proposed MP& M operations segregate their wastewaters by type and treat them in preliminary treatment systems. After preliminary treatment, facilities performing proposed MP& M operations usually commingle the wastewater with other process wastewater and treat the commingled wastewater in an end of pipe treatment system. Generally, the end of pipe treatment consists of chemical precipitation and sedimentation ( see Section 8.5.1). When high concentrations of metals are present in the wastewater, sites may use preliminary batch chemical precipitation and sedimentation to ensure that the high concentrations do not cause an upset in the end of pipe treatment system. Facilities performing proposed MP& M operations may also contract haul concentrated baths to centralized waste treatment facilities. Table C 10 summarizes the pollutant concentration data obtained from sampling the influent to end of pipe chemical precipitation with sedimentation and chemical precipitation with membrane filtration systems for metal bearing wastewater.

C 7 Appendix C  Wastewater Characteristics Table C 7 Number of Process Water and Rinse Water Samples Collected and Analyzed for Unit Operations That Generate Metal Bearing Wastewater Unit Operation No. of Process Water Samples a No. of Rinse Water Samples a Abrasive Jet Machining Acid Treatment without Chromium Anodizing without Chromium Carbon Black Deposition Chemical Milling Chemical Conversion Coating without Chromium Electrochemical Machining Electroless Plating Electrolytic Cleaning Electroplating without Chromium or Cyanide Electropolishing Painting immersion ( Including Electrophoretic, " E coat")

Photo Image Developing Photoresist Applications Plasma Arc Machining Salt Bath Descaling Solder Flux Cleaning Solder Fusing Stripping ( paint)

Stripping ( metallic coating) 3 27 4 2 4 24 1 9 9 24 1 1 5 0 1 0 1 0 6 9 3 65 3 3 9 59 2 28 17 48 1 6 11 0 0 4 4 3 4 12 Source: MP& M Sampling Program. a Unit operations for which no samples were collected are rarely performed or were not observed at facilities performing proposed MP& M operations.

C 8 Appendix C  Wastewater Characteristics Table C 8 Process Water Pollutant Concentration Data for Unit Operations That Generate Metal Bearing Wastewater Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Organic Priority Pollutants 1,1 Dichloroethane 41 0 NA NA NA NA 1,1 Dichloroethene 41 0 NA NA NA NA 1,1,1 Trichloroethane 41 0 NA NA NA NA 2 Nitrophenol 40 1 2.15 2.15 2.15 2.15 2,4 Dinitrophenol 36 1 335 335 335 335 2,4 Dimethylphenol 40 1 0.167 0.167 0.167 0.167 2,6 Dinitrotoluene 41 2 0.605 6.98 3.79 3.79 4 Chloro 3 Methylphenol 39 0 NA NA NA NA 4 Nitrophenol 39 1 14.1 14.1 14.1 14.1 Acenaphthene 41 0 NA NA NA NA Acrolein 40 1 0.591 0.591 0.591 0.591 Anthracene 41 0 NA NA NA NA Bis( 2 ethylhexyl) Phthalate 41 12 0.012 18.2 3.10 0.291 Butyl Benzyl Phthalate 41 0 NA NA NA NA Chlorobenzene 41 4 0.011 1.56 0.414 0.041 Chloroethane 41 0 NA NA NA NA Chloroform 41 3 0.012 0.218 0.080 0.012 Di n octyl Phthalate 41 2 0.639 1.42 1.03 1.03 Di n butyl Phthalate 41 0 NA NA NA NA Dimethyl Phthalate 41 0 NA NA NA NA Ethylbenzene 41 2 0.020 2.91 1.46 1.46 Fluoranthene 41 0 NA NA NA NA Fluorene 41 0 NA NA NA NA Isophorone 41 0 NA NA NA NA Methylene Chloride 41 3 0.011 0.173 0.080 0.056 N Nitrosodimethylamine 41 1 6.67 6.67 6.67 6.67 N Nitrosodiphenylamine 41 0 NA NA NA NA C 9 Appendix C  Wastewater Characteristics Table C 8 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Organic Priority Pollutants ( continued)

Naphthalene 41 2 0.024 0.208 0.116 0.116 Phenanthrene 41 0 NA NA NA NA Phenol 41 5 0.024 1,044 216 2.00 Pyrene 41 0 NA NA NA NA Tetrachloroethene 41 0 NA NA NA NA Toluene 41 2 0.014 0.032 0.023 0.023 Trichloroethene 41 6 0.010 0.058 0.026 0.023 Metal Priority Pollutants Antimony 129 50 0.002 3.56 0.359 0.090 Arsenic 129 62 0.001 16.4 0.655 0.080 Beryllium 129 39 0.001 3.87 0.270 0.030 Cadmium 132 74 0.002 57,100 791 0.203 Chromium 132 115 0.007 108,000 1,952 1.87 Copper 132 124 0.009 141,000 2,885 7.24 Lead 132 83 0.002 4,880 120 2.62 Mercury 129 25 0.0003 0.032 0.003 0.0009 Nickel 131 109 0.007 84,623 3,091 5.89 Selenium 129 30 0.001 8.00 0.659 0.051 Silver 132 57 0.001 14.4 0.503 0.075 Thallium 129 18 0.001 3.48 0.411 0.019 Zinc 131 118 0.005 53,200 2,750 15.7 Conventional Pollutants BOD 5 Day ( Carbonaceous) 33 22 4.29 18,600 4,537 1,600 Oil and Grease ( as HEM) 53 27 1.08 2,400 271 68.9 Total Suspended Solids 127 119 5.00 110,000 2,338 154 Nonconventional Organic Pollutants 1 Bromo 2 Chlorobenzene 41 4 0.012 0.978 0.382 0.268 1 Bromo 3 Chlorobenzene 41 4 0.031 0.490 0.193 0.126 1 Methylfluorene 41 0 NA NA NA NA 1 Methylphenanthrene 41 0 NA NA NA NA 1,4 Dioxane 41 3 0.365 2.80 1.36 0.920 C 10 Appendix C  Wastewater Characteristics Table C 8 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Nonconventional Organic Pollutants ( continued)

2 Butanone 40 12 0.070 26.1 4.61 1.43 2 Hexanone 41 1 5.02 5.02 5.02 5.02 2 Isopropylnaphthalene 41 0 NA NA NA NA 2 Methylnaphthalene 41 1 0.220 0.220 0.220 0.220 2 Propanone 41 27 0.052 250 11.3 0.485 3,6 Dimethylphenanthrene 41 0 NA NA NA NA 4 Methyl 2 Pentanone 41 5 0.052 159 32.0 0.187 Acetophenone 41 0 NA NA NA NA Alpha terpineol 41 0 NA NA NA NA Aniline 41 4 0.015 0.335 0.145 0.115 Benzoic Acid 41 8 0.051 8,098 1,037 27.2 Benzyl Alcohol 41 4 0.012 0.278 0.103 0.061 Biphenyl 41 0 NA NA NA NA Carbon Disulfide 41 1 0.053 0.053 0.053 0.053 Dibenzofuran 41 1 0.140 0.140 0.140 0.140 Dibenzothiophene 41 0 NA NA NA NA Diphenyl Ether 41 0 NA NA NA NA Diphenylamine 41 0 NA NA NA NA Hexanoic Acid 41 5 0.012 31.5 9.12 0.763 Isobutyl Alcohol 41 0 NA NA NA NA m Xylene 14 2 0.020 5.06 2.54 2.54 m+ p Xylene 27 0 NA NA NA NA Methyl Methacrylate 41 4 0.181 0.797 0.586 0.682 n Decane 41 1 3.51 3.51 3.51 3.51 n Docosane 41 1 0.142 0.142 0.142 0.142 n Dodecane 41 1 1.27 1.27 1.27 1.27 n Eicosane 41 1 0.030 0.030 0.030 0.030 n Hexacosane 41 1 0.106 0.106 0.106 0.106 n Hexadecane 41 0 NA NA NA NA n Nitrosopiperidine 41 0 NA NA NA NA n Octacosane 41 1 0.071 0.071 0.071 0.071 C 11 Appendix C  Wastewater Characteristics Table C 8 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Nonconventional Organic Pollutants ( continued)

n Octadecane 41 0 NA NA NA NA n Tetracosane 41 1 0.097 0.097 0.097 0.097 n Tetradecane 41 0 NA NA NA NA n Triacontane 41 1 0.082 0.082 0.082 0.082 n, n Dimethylformamide 41 3 0.032 0.123 0.064 0.036 o cresol 41 2 0.023 0.195 0.109 0.109 o xylene 27 0 NA NA NA NA o+ p Xylene 14 2 0.910 2.01 1.46 1.46 p Cymene 41 0 NA NA NA NA p Cresol 41 3 0.011 0.513 0.192 0.054 Pyridine 41 0 NA NA NA NA Styrene 41 0 NA NA NA NA Trichlorofluoromethane 41 0 NA NA NA NA Tripropyleneglycol Methyl Ether 41 2 0.245 1.45 0.848 0.848 Nonconventional Metal Pollutants Aluminum 131 107 0.042 34,900 1,112 3.39 Barium 129 102 0.001 259 4.24 0.096 Boron 130 106 0.022 17,800 659 1.32 Calcium 129 125 0.054 2,250 130 23.4 Cobalt 129 81 0.003 4,700 73.5 0.660 Gold 1 1 0.392 0.392 0.392 0.392 Iron 131 122 0.011 374,000 7,051 13.4 Magnesium 129 106 0.085 960 73.8 15.2 Manganese 132 110 0.001 4,790 106 0.767 Molybdenum 130 87 0.001 197 5.40 0.237 Sodium 129 125 1.25 383,000 17,905 1,164 Tin 132 82 0.004 22,670 930 0.984 Titanium 129 84 0.002 13,250 180 0.303 Vanadium 129 68 0.001 1,495 23.5 0.066 Yttrium 129 24 0.001 0.900 0.115 0.038 C 12 Appendix C  Wastewater Characteristics Table C 8 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Other Nonconventional Pollutants Ammonia as Nitrogen 66 53 0.060 44,800 2,922 10.0 Chemical Oxygen Demand ( COD) 60 56 83.0 600,000 32,426 7,400 Chloride 69 53 1.00 328,300 20,901 240 Cyanide 10 7 0.027 0.510 0.153 0.120 Fluoride 69 58 0.140 55,500 1,034 5.10 Hexavalent Chromium 36 5 0.008 0.430 0.104 0.025 Sulfate 105 89 1.56 755,000 36,919 808 Total Dissolved Solids 125 123 87.0 1,000,000 135,033 64,100 Total Kjeldahl Nitrogen 49 42 0.480 40,000 2,584 42.0 Total Organic Carbon ( TOC) 49 48 4.71 54,000 7,492 1,245 Total Petroleum Hydrocarbons ( as SGT HEM) 51 9 6.00 352 88.2 14.1 Total Phosphorus 30 21 0.020 11,000 945 11.0 Total Recoverable Phenolics 52 35 0.006 135 7.78 0.330 Total Sulfide 17 0 NA NA NA NA Source: MP& M Sampling Program. a Due to budgetary constraints, EPA did not analyze all samples for all pollutants. NA  Not applicable.

C 13 Appendix C  Wastewater Characteristics Table C 9 Rinse Water Pollutant Concentration Data for Unit Operations That Generate Metal Bearing Wastewater Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Organic Priority Pollutants 1,1 Dichloroethane 91 0 NA NA NA NA 1,1 Dichloroethene 91 0 NA NA NA NA 1,1,1 Trichloroethane 91 0 NA NA NA NA 2 Nitrophenol 89 0 NA NA NA NA 2,4 Dimethylphenol 91 0 NA NA NA NA 2,4 Dinitrophenol 85 0 NA NA NA NA 2,6 Dinitrotoluene 91 0 NA NA NA NA 4 Chloro 3 Methylphenol 91 0 NA NA NA NA 4 Nitrophenol 88 0 NA NA NA NA Acenaphthene 91 0 NA NA NA NA Acrolein 87 0 NA NA NA NA Anthracene 91 0 NA NA NA NA Bis( 2 ethylhexyl) Phthalate 91 10 0.011 0.281 0.064 0.019 Butyl Benzyl Phthalate 91 0 NA NA NA NA Chlorobenzene 91 0 NA NA NA NA Chloroethane 91 0 NA NA NA NA Chloroform 91 49 0.010 0.063 0.025 0.022 Di n octyl Phthalate 91 1 0.013 0.013 0.013 0.088 Di n butyl Phthalate 91 6 0.014 0.190 0.098 0.013 Dimethyl Phthalate 91 1 0.021 0.021 0.021 0.021 Ethylbenzene 91 2 0.021 0.028 0.024 0.024 Fluoranthene 91 0 NA NA NA NA Fluorene 91 0 NA NA NA NA Isophorone 91 0 NA NA NA NA Methylene Chloride 91 1 0.011 0.011 0.011 0.011 n Nitrosodiphenylamine 91 0 NA NA NA NA n Nitrosodimethylamine 91 0 NA NA NA NA Naphthalene 91 1 0.021 0.021 0.021 0.021 C 14 Appendix C  Wastewater Characteristics Table C 9 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Organic Priority Pollutants ( continued)

Phenanthrene 91 0 NA NA NA NA Phenol 90 5 0.011 2.00 0.417 0.024 Pyrene 91 0 NA NA NA NA Tetrachloroethene 91 0 NA NA NA NA Toluene 91 0 NA NA NA NA Trichloroethene 91 3 0.010 0.018 0.015 0.015 Metal Priority Pollutants Antimony 261 42 0.002 0.158 0.026 0.011 Arsenic 261 63 0.001 0.308 0.018 0.006 Beryllium 261 13 0.001 0.059 0.010 0.001 Cadmium 265 62 0.002 6.93 0.310 0.011 Chromium 265 155 0.002 21.6 0.761 0.052 Copper 265 235 0.003 507 14.0 0.154 Lead 265 90 0.002 81.0 3.52 0.066 Mercury 261 25 0.0002 0.004 0.001 0.0004 Nickel 263 172 0.002 437 20.0 0.115 Selenium 261 39 0.001 0.412 0.019 0.003 Silver 265 55 0.001 0.962 0.047 0.010 Thallium 261 19 0.001 0.039 0.006 0.001 Zinc 265 187 0.002 13,700 168 0.019 Conventional Pollutants BOD 5 Day ( Carbonaceous) 86 39 1.07 11,400 505 40.0 Oil and Grease ( as HEM) 130 34 1.12 114 17.2 10.4 Total Suspended Solids 260 174 2.00 6,920 132 20.0 Nonconventional Organic Pollutants 1 Bromo 2 Chlorobenzene 91 0 NA NA NA NA 1 Bromo 3 Chlorobenzene 91 0 NA NA NA NA 1 Methylfluorene 91 0 NA NA NA NA 1 Methylphenanthrene 91 0 NA NA NA NA 1,4 Dioxane 91 1 0.196 0.196 0.196 0.196 2 Butanone 89 10 0.066 0.550 0.214 0.133 C 15 Appendix C  Wastewater Characteristics Table C 9 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Nonconventional Organic Pollutants ( continued)

2 Hexanone 91 0 NA NA NA NA 2 Isopropylnaphthalene 91 0 NA NA NA NA 2 Methylnaphthalene 91 0 NA NA NA NA 2 Propanone 91 13 0.052 11.5 1.51 0.097 3,6 Dimethylphenanthrene 91 0 NA NA NA NA 4 Methyl 2 Pentanone 91 2 0.190 17.4 8.80 8.80 Acetophenone 91 0 NA NA NA NA Alpha Terpineol 91 0 NA NA NA NA Aniline 91 0 NA NA NA NA Benzoic Acid 91 6 0.108 4.31 1.21 0.659 Benzyl Alcohol 91 2 0.014 0.014 0.014 0.014 Biphenyl 91 0 NA NA NA NA Carbon Disulfide 91 0 NA NA NA NA Dibenzofuran 91 0 NA NA NA NA Dibenzothiophene 91 0 NA NA NA NA Diphenyl Ether 91 1 0.013 0.013 0.013 0.013 Diphenylamine 91 0 NA NA NA NA Hexanoic Acid 91 1 0.015 0.015 0.015 0.015 Isobutyl Alcohol 91 0 NA NA NA NA m Xylene 20 2 0.036 0.076 0.056 0.056 m+ p Xylene 71 0 NA NA NA NA Methyl Methacrylate 91 0 NA NA NA NA n Decane 91 0 NA NA NA NA n Docosane 91 1 0.012 0.012 0.012 0.012 n Dodecane 91 0 NA NA NA NA n Eicosane 91 0 NA NA NA NA n Hexacosane 91 2 0.037 0.434 0.236 0.236 n Hexadecane 91 1 0.057 0.057 0.057 0.057 n Nitrosopiperidine 91 0 NA NA NA NA n Octacosane 91 1 0.041 0.041 0.041 0.041 n Octadecane 91 0 NA NA NA NA C 16 Appendix C  Wastewater Characteristics Table C 9 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Nonconventional Organic Pollutants ( continued)

n Tetracosane 91 1 0.018 0.018 0.018 0.018 n Tetradecane 91 1 0.221 0.221 0.221 0.221 n Triacontane 91 2 0.030 0.477 0.253 0.253 n, n dimethylformamide 91 2 0.026 0.115 0.071 0.071 o Cresol 91 0 NA NA NA NA o Xylene 71 0 NA NA NA NA o+ p Xylene 20 2 0.042 0.113 0.077 0.077 p Cymene 91 0 NA NA NA NA p Cresol 91 0 NA NA NA NA Pyridine 91 0 NA NA NA NA Styrene 91 0 NA NA NA NA Trichlorofluoromethane 91 0 NA NA NA NA Tripropyleneglycol Methyl Ether 91 1 8.48 8.48 8.48 8.48 Nonconventional Metal Pollutants Aluminum 263 161 0.022 76.9 1.61 0.192 Barium 261 207 0.001 2.90 0.064 0.028 Boron 263 179 0.016 363 4.38 0.180 Calcium 261 255 0.033 361 30.7 23.0 Cobalt 261 58 0.001 12.4 0.945 0.014 Gold 2 1 6.88 6.88 6.88 6.88 Iron 263 196 0.003 2,810 58.8 0.334 Magnesium 261 240 0.067 130 9.22 7.56 Manganese 265 171 0.001 68.3 1.52 0.024 Molybdenum 263 80 0.002 13.4 0.341 0.017 Sodium 261 257 0.277 55,800 710 60.0 Tin 265 105 0.002 828 11.6 0.052 Titanium 261 80 0.001 18.1 0.762 0.015 Vanadium 261 35 0.001 1.10 0.108 0.010 Yttrium 261 8 0.001 0.004 0.002 0.001 C 17 Appendix C  Wastewater Characteristics Table C 9 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Other Nonconventional Pollutants Amenable Cyanide 3 3 0.340 1.97 1.05 0.830 Ammonia as Nitrogen 114 68 0.050 1,190 91.2 1.58 Chemical Oxygen Demand ( COD) 107 84 5.20 20,400 614 44.0 Chloride 77 76 1.20 5,000 219 26.0 Cyanide 12 9 0.028 87.0 10.7 0.830 Fluoride 77 68 0.110 60.0 3.65 0.990 Hexavalent Chromium 90 17 0.011 0.063 0.023 0.019 Sulfate 163 158 1.64 7,120 306 54.0 Total Dissolved Solids 258 258 10.0 132,000 2,469 550 Total Kjeldahl Nitrogen 79 44 0.100 395 28.0 8.69 Total Organic Carbon ( TOC) 129 114 1.16 6,110 230 12.0 Total Petroleum Hydrocarbons ( as SGT HEM) 129 7 5.25 13.0 7.86 7.75 Total Phosphorus 28 21 0.026 290 30.9 1.40 Total Recoverable Phenolics 100 42 0.005 2.85 0.192 0.013 Total Sulfide 45 0 NA NA NA NA Source: MP& M Sampling Data. a Due to budgetary constraints, EPA did not analyze all samples for all pollutants. NA  Not applicable.

C 18 Appendix C  Wastewater Characteristics Table C 10 Pollutant Concentration Data for the Influent to Chemical Precipitation Systems Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Organic Priority Pollutants 1,1 Dichloroethane 171 0 NA NA NA NA 1,1 Dichloroethylene 171 2 0.011 0.748 0.379 0.379 1,1,1 Trichloroethane 171 6 0.019 0.084 0.053 0.053 2,4 Dimethylphenol 162 0 NA NA NA NA 2,4 Dinitrophenol 167 2 0.111 1.66 0.885 0.885 2,6 Dinitrotoluene 178 0 NA NA NA NA 2 Nitrophenol 177 0 NA NA NA NA 4 Chloro m Cresol 176 9 0.011 1.14 0.183 0.076 4 Nitrophenol 172 0 NA NA NA NA Acenaphthene 178 0 NA NA NA NA Acrolein 141 0 NA NA NA NA Anthracene 178 1 0.104 0.104 0.104 0.104 Benzyl Butyl Phthalate 178 2 0.009 0.010 0.009 0.009 Bis( 2 ethylhexyl) Phthalate 178 43 0.008 0.298 0.052 0.030 Chlorobenzene 171 0 NA NA NA NA Chloroethane 171 0 NA NA NA NA Chloroform 171 68 0.010 0.824 0.097 0.031 Di n butyl Phthalate 178 6 0.007 0.066 0.030 0.018 Di n octyl Phthalate 178 1 0.012 0.012 0.012 0.012 Dimethyl Phthalate 175 1 0.0004 0.0004 0.0004 0.0004 Ethylbenzene 171 5 0.006 0.335 0.074 0.010 Fluoranthene 178 0 NA NA NA NA Fluorene 178 1 0.045 0.045 0.045 0.045 Isophorone 175 0 NA NA NA NA Methylene Chloride 171 10 0.008 0.172 0.043 0.023 n Nitrosodimethylamine 175 2 0.065 0.070 0.067 0.067 n Nitrosodiphenylamine 174 0 NA NA NA NA C 19 Appendix C  Wastewater Characteristics Table C 10 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Organic Priority Pollutants ( continued)

Naphthalene 178 3 0.012 0.054 0.035 0.038 Phenanthrene 178 3 0.041 0.112 0.071 0.060 Phenol 179 34 0.010 0.634 0.070 0.030 Pyrene 178 0 NA NA NA NA Tetrachloroethene 171 8 0.015 1.11 0.306 0.081 Toluene 171 6 0.009 2.77 0.534 0.019 Trichloroethylene 171 3 0.019 0.023 0.021 0.021 Metal Priority Pollutants Antimony 261 86 0.002 1.13 0.058 0.018 Arsenic 268 109 0.001 0.530 0.025 0.009 Beryllium 268 64 0.0002 3.23 0.228 0.004 Cadmium 457 170 0.0003 323 4.25 0.039 Chromium 469 444 0.001 1,350 9.92 0.676 Copper 472 467 0.010 665 13.9 0.480 Lead 465 376 0.002 159 3.44 0.416 Mercury 266 52 0.00003 0.012 0.001 0.0003 Nickel 467 457 0.012 2,101 18.3 1.47 Selenium 265 42 0.001 0.090 0.018 0.006 Silver 460 222 0.001 4.94 0.406 0.036 Thallium 265 26 0.001 0.112 0.011 0.002 Zinc 472 459 0.009 636 33.6 3.65 Conventional Pollutants BOD 5 Day ( Carbonaceous) 133 86 2.40 609 64.4 26.0 Oil and Grease ( as HEM) 236 159 0.570 32,000 428 12.1 Total Suspended Solids 334 314 4.00 11,400 803 120 Nonconventional Organic Pollutants 1,4 Dioxane 166 6 0.033 2.41 0.788 0.584 1 Bromo 2 Chlorobenzene 169 2 0.011 0.012 0.012 0.012 1 Bromo 3 Chlorobenzene 169 5 0.026 0.067 0.045 0.038 1 Methylfluorene 169 2 0.111 0.189 0.150 0.150 1 Methylphenanthrene 169 2 0.092 0.181 0.136 0.136 C 20 Appendix C  Wastewater Characteristics Table C 10 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Nonconventional Organic Pollutants ( continued)

2 Butanone 166 13 0.056 2.45 0.668 0.151 2 Hexanone 166 0 NA NA NA NA 2 Isopropylnaphthalene 169 0 NA NA NA NA 2 Methylnaphthalene 173 2 0.076 0.205 0.140 0.140 2 Propanone 166 87 0.051 16.7 0.822 0.137 3,6 Dimethylphenanthrene 169 2 0.019 0.062 0.041 0.041 4 Methyl 2 Pentanone 166 10 0.120 1.36 0.308 0.181 Acetophenone 169 2 0.010 0.011 0.011 0.011 Alpha terpineol 162 5 0.013 0.087 0.051 0.054 Aniline 173 6 0.013 0.052 0.023 0.017 Benzoic Acid 173 69 0.011 34.8 3.27 0.229 Benzyl Alcohol 173 9 0.005 0.080 0.028 0.013 Biphenyl 169 1 0.011 0.011 0.011 0.011 Carbon Disulfide 166 10 0.016 3.92 0.505 0.058 Dibenzofuran 173 0 NA NA NA NA Dibenzothiophene 169 2 0.015 0.025 0.020 0.020 Diphenyl Ether 169 0 NA NA NA NA Diphenylamine 165 1 0.033 0.033 0.033 0.033 Hexanoic Acid 169 23 0.010 0.461 0.053 0.017 Isobutyl Alcohol 166 0 NA NA NA NA m+ p Xylene 96 0 NA NA NA NA m Xylene 70 1 0.016 0.016 0.016 0.016 Methyl Methacrylate 166 3 0.019 0.039 0.030 0.032 n Decane 166 3 0.029 0.031 0.031 0.031 n Docosane 169 6 0.011 0.026 0.016 0.013 n Dodecane 168 6 0.044 0.772 0.269 0.101 n Eicosane 169 17 0.010 0.181 0.034 0.020 n Hexacosane 169 12 0.012 0.041 0.027 0.028 n Hexadecane 169 22 0.010 0.631 0.085 0.026 n Nitrosopiperidine 169 0 NA NA NA NA n octacosane 169 3 0.018 0.036 0.030 0.035 C 21 Appendix C  Wastewater Characteristics Table C 10 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Nonconventional Organic Pollutants ( continued)

n Octadecane 169 25 0.011 0.493 0.072 0.024 n Tetracosane 169 7 0.012 0.032 0.019 0.017 n Tetradecane 169 14 0.016 1.01 0.174 0.058 n Triacontane 169 4 0.011 0.031 0.019 0.017 n, n Dimethylformamide 169 22 0.011 0.581 0.094 0.044 o+ p Xylene 70 3 0.013 0.023 0.017 0.014 o Cresol 169 0 NA NA NA NA o Xylene 96 0 NA NA NA NA p Cresol 169 10 0.013 0.030 0.019 0.017 p Cymene 169 3 0.015 0.054 0.030 0.02 Pyridine 169 0 NA NA NA NA Styrene 173 8 0.010 0.188 0.041 0.022 Trichlorofluoromethane 171 6 0.029 0.109 0.045 0.033 Tripropyleneglycol Methyl Ether 169 23 0.064 5.21 1.83 1.05 Nonconventional Metal Pollutants Aluminum 268 246 0.055 132 8.68 2.38 Barium 266 241 0.003 9.91 0.251 0.058 Boron 253 232 0.057 81.3 3.53 0.787 Calcium 268 268 3.40 1,220 83.0 34.9 Cobalt 264 121 0.001 25.8 0.757 0.019 Gold 20 10 0.013 0.150 0.056 0.038 Iron 268 268 0.022 3,880 111 5.38 Magnesium 268 263 0.349 3,360 74.5 8.88 Manganese 453 452 0.001 109 4.04 0.870 Molybdenum 453 347 0.001 3.06 0.175 0.037 Sodium 268 268 17.7 9,600 460 211 Tin 442 341 0.004 1,440 14.2 0.199 Titanium 253 189 0.002 76.4 1.53 0.048 Vanadium 264 87 0.002 1.19 0.052 0.014 Yttrium 253 60 0.001 0.085 0.010 0.004 C 22 Appendix C  Wastewater Characteristics Table C 10 ( Continued)

Pollutant No. of Samples Analyzeda No. of Detects Concentration ( mg/ L)

Minimum Maximum Mean Median Other Nonconventional Pollutants Ammonia as Nitrogen 113 110 0.040 320 25.9 5.61 Chemical Oxygen Demand ( COD) 203 194 1.50 13,000 532 122 Chloride 78 75 4.50 9,500 338 140 Cyanide 32 12 0.008 0.096 0.022 0.012 Fluoride 78 77 0.130 100 4.54 1.50 Hexavalent Chromium 133 50 0.010 21.0 0.771 0.060 Sulfate 177 170 18.0 6,125 469 318 Total Dissolved Solids 263 263 19.0 34,000 2,325 1,103 Total Kjeldahl Nitrogen 83 80 0.110 160 14.9 6.66 Total Organic Carbon ( TOC) 175 146 3.57 400 73.5 46.9 Total Petroleum Hydrocarbons ( as SGT HEM) 143 52 5.00 93.0 20.4 10.0 Total Phosphorus 84 82 0.020 525 28.1 5.20 Total Recoverable Phenolics 188 110 0.006 13.0 0.387 0.047 Total Sulfide 95 31 0.150 28.0 5.20 1.03 Ziram 5 3 0.177 0.448 0.291 0.247 Source: MP& M Sampling Program. a Due to budgetary constraints, EPA did not analyze all samples for all pollutants. NA  Not applicable.

C 23 Appendix D  Pollution Prevention and Water Conservation Practices Appendix D POLLUTION PREVENTION AND WATER CONSERVATION PRACTICES Appendix D  Pollution Prevention and Water Conservation Practices Appendix D POLLUTION PREVENTION AND WATER CONSERVATION PRACTICES EPA observed a number of pollution prevention and water conservation practices during site visits and sampling episodes, and MP& M surveys provided additional information on these practices ( see Sections 3.0 and 8.0). Some common pollution prevention and water conservation methods for surface treatment include drag out tanks, countercurrent cascade rinsing, manual and automatic rinse water shut off, timed rinses, flow restrictors, conductivity meters, and in process ion exchange and water recycle. In this appendix, EPA describes some of these common pollution prevention and water conservation methods used by facilities evaluated for the final rule (  MP& M facilities ) as a measure to assist a broader audience to achieve improved environmental performance and compliance, pollution prevention through source reduction, and continual improvement. EPA is not promulgating or requiring any of these methods or mass based limitations and standards in the MP& M effluent guidelines ( see Section 15.0). The final limitations and standards in the MP& M effluent guidelines are concentration based and may be achieved using any method compliant with EPA regulations.

Pollution Prevention and Water Conservation Practices for Surface Treatment The Agency identified four categories of pollution prevention and water conservation practices and technologies that can be applied to reduce rinse water use: drag out reduction and/ or drag out recovery methods; improved rinse tank design and rinsing configurations; rinse water use control devices; and, metal recovery and rinse water reuse technologies. Surface treatment rinses include those following acid and alkaline treatment, anodizing, electroplating, electroless plating, and chemical conversion coating. Rinsing dilutes and removes the chemical film of drag out remaining on parts and racks after processing in a chemical bath. In addition to conserving water use, some of these methods ( especially those that affect drag out and recover chemicals) also conserve raw materials, reduce pollutant loadings to wastewater treatment systems, and reduce treatment reagent requirements and sludge production. Within each of these categories are several specific practices and technologies. Table D 1 presents examples of these practices and technologies, as well as their applicability to the MP& M operations. 1 Table D 2 provides descriptions of these practices.

1EPA evaluated a number of unit operations for the May 1995 proposal, January 2001 proposal, and June 2002 NODA ( see Tables 4 3 and 4 4). However, EPA selected a subset of these unit operations for regulation in the final rule ( see Section 1.0). For this Section, the term   proposed MP& M operations  means those operations evaluated for the two proposals, NODA, and final rule. The term   final MP& M operations  means those operations defined as   oily operations  ( see Section 1.0, 40 CFR 438.2( f), and Appendix B to Part 438) and regulated by the final rule.

D 1 D. 1 Appendix D  Pollution Prevention and Water Conservation Practices D 2 Table D 1 Potential Water Conservation Methods for Surface Treatment Rinses Practice Alkaline Clean Acid Clean Hexavalent Chromium Trivalent Chromium Cadmium Zinc Cyanide Cadmium Zinc Non

Cyanide Acid Copper Copper Cyanide Watts, Woods,

Other Nickels Electro less Nickel Silver Cyanide Gold Cyanide Lead, Lead

Tin Tin Chrom ate Phos phate Chromic AcidAnodize Sulfuric Anodize Drag out Reduction and Recovery Fog or spray rinsing over tank ( 110 ° F or higher)                 a     Controlled slow withdrawal                                     Addition of wetting agent ( when compatible)                                 Positioning work piece                                     Long drip time                                 Drip shield                                     Air knife                       Drag out tank ( heated)                               Drag in/ out tank                               Lowest concentration                                     Highest temperature                                   Rinse Tank Design and Innovative Configuration Countercurrent rinse                                     Cascading rinse ( cleaning)     Spray rinse                                     Good tank designb                                     Rinse Water Use Control Flow restrictors                                     Timer controls                                     Conductivity controls                                     Appendix D  Pollution Prevention and Water Conservation Practices Table D 1 ( Continued)

Practice Alkaline Clean Acid Clean Hexavalent Chromium Trivalent Chromium Cadmium Zinc Cyanide Cadmium Zinc Non

Cyanide Acid Copper Copper Cyanide Watts, Woods,

Other Nickels Electro less Nickel Silver Cyanide Gold Cyanide Lead, Lead

Tin Tin Chrom ate Phos phate Chromic AcidAnodize Sulfuric Anodize Metal Recovery and Rinse Water Reuse Technologies Evaporatorc                               Ion exchangec                     Electrolytic Recovery                 Electrodialysisc         Reverse osmosisc                 Source: MP& M Site Visits, MP& M Surveys, Technical Literature.

a Alkaline tin only.

b For example, air or other agitation, minimum size, and inlet, outlet location opposite ends.

c Only common applications of this technology are checked.

D 3 Appendix D  Pollution Prevention and Water Conservation Practices Table D 2 Descriptions of Pollution Prevention and Water Conservation Practices and Technologies Practice or Technology Description Air Knife Air knives are usually installed over a process tank or drip shield and are designed to remove drag out by blowing it off the surface of parts and racks. Drag out is routed back to the process tank. Air knives are more effective with flat parts. They cannot be used to dry surfaces that passivate or stain due to oxidation.

Cascade Rinsing Cascade rinsing is a method of reusing rinse water. Water from one rinsing operation is plumbed to another, less critical one before being discharged to treatment. Some rinse waters acquire chemical properties, such as low pH, that make them desirable for reuse in specific rinse systems. This is generally referred to as reactive rinsing.

Conductivity Controller Conductivity probes measure the conductivity of water in a rinse tank to regulate the flow of fresh water into the rinse system. Conductivity controllers consist of a controller, a meter with adjustable set points, a probe that is placed in the rinse tank, and a solenoid valve. As parts are rinsed, dissolved solids are added to the water in the rinse tank, raising the conductivity of the water. When conductivity reaches the set point, the solenoid valve opens to allow make up water to enter the tank. When the conductivity falls below the set point, the valve shuts to discontinue the make up water.

In theory, conductivity control of rinse flow is a precise method of maintaining optimum rinsing conditions in intermittently used rinse operations. In practice, conductivity controllers work best with deionized rinse water. Incoming water conductivity may vary day to day and season to season, which forces frequent set point adjustments. Suspended solids and nonionic contaminants ( e. g., oil) are not detected by the conductivity probe and can cause inadequate rinsing.

Countercurrent Cascade Rinsing Countercurrent cascade rinsing refers to a series of consecutive rinse tanks that are plumbed to cause water to flow from one tank to another in the direction opposite of the work flow. Countercurrent cascade rinsing is widely used to reduce the discharge rate of rinse water. Fresh water flows into the rinse tank located farthest from the process tank and overflows, in turn, to the rinse tanks closer to the process tank. This technique is termed countercurrent rinsing, because the part and the rinse water move in opposite directions. Over time, the first rinse becomes contaminated with drag out and reaches a stable concentration that is lower than the process solution. The second rinse stabilizes at a lower concentration, which enables less rinse water to be used than if only one rinse tank were in place. The more countercurrent cascade rinse tanks ( three stage, four stage, etc.), the less water is needed to adequately remove the process solution.

Drag in/ Drag out Rinsing A drag in/ drag out rinse system may be a single tank or two tanks plumbed together. Parts enter the rinse system before and after processing in the bath. As parts enter the process bath, they drag in process chemicals present in the drag in/ drag out rinse rather than plain rinse water. This rinsing configuration is an effective recovery method for process baths that have low evaporation rates.

D 4 Appendix D  Pollution Prevention and Water Conservation Practices Table D 2 ( Continued)

Practice or Technology Description Drag out Tank Drag out tanks are rinse tanks that are initially filled with water and remain stagnant. Parts are rinsed in drag out tanks directly after exiting the process bath. Gradually, the concentration of process chemicals in the drag out tank rises. In the most efficient configuration, a drag out tank is used after a heated process tank that has a moderate to high evaporation rate. Part of the fluid in the drag out tank is returned to the process tank to replace the evaporative loss. The level of fluid in the drag out tank is maintained by adding fresh water.

Drip Shields Drip shields are installed between process tanks and rinse tanks to recover process fluid dripping off racks and barrels that would otherwise fall into rinse tanks or onto the floor. Often, drip shields are an inclined piece of polypropylene or other material that is inert to the process.

Drip Tanks Drip tanks are similar to drag out tanks except they are not filled with water. Parts exiting a process bath are held over the drip tank and the process fluid that drips from the parts is collected in the tank. When enough fluid is collected in the drip tank, it is returned to the process tank. Drip tanks are generally considered to be a less effective drag out recovery practice than using drag out tanks.

Electrodialysis Electrodialysis is a membrane technology used to remove impurities from and recover process solutions. With this technology, a direct current is applied across a series of alternating anion and cation exchange membranes to remove dissolved metal salts and other ionic constituents from solutions.

An electrodialysis unit consists of a rectifier and a membrane stack. The stack consists of alternating anion and cation specific membranes that form compartments. As the feed stream enters the unit, each alternating membrane compartment becomes filled with either dilute or concentrate. When the compartments are filled, a direct current is applied across the membrane. Cations in a dilute compartment traverse one cation specific membrane in the direction of the cathode, and are trapped in that compartment by the next membrane, which is anion specific. Anions from the neighboring dilute compartment traverse the anion specific membrane in the direction of the anode, joining the cations, and are likewise trapped in the concentrate compartment by the next cation specific membrane. In this way, the feed stream is depleted of ions, and anions and cations are trapped in each concentrate compartment.

The feed stream is often from the first rinse tank in a countercurrent series, with a concentration of 5 gallons per liter ( g/ L) or more of total dissolved solids ( TDS). The concentrate, with a TDS concentration of 50 g/ L or more and a volume of less than 10% of the feed stream, is returned to the process. The dilute, representing more than 90% of the feed stream at a TDS concentration of typically 1 g/ L or less, is recycled as rinse water or discharged to treatment.

D 5 Appendix D  Pollution Prevention and Water Conservation Practices Table D 2 ( Continued)

Practice or Technology Description Electrolytic Recovery ( Electrowinning) Electrolytic recovery is an electrochemical process used to recover metals from many types of process solutions, such as electroplating rinse waters and baths. Electrolytic recovery removes metal ions from a wastestream by processing the stream in an electrolytic cell, which consists of a closely spaced anode and cathode. Commercial equipment consists of several cells, a transfer pump, and a rectifier. Current is applied across the cell and metal cations are deposited on the cathodes. The wastestream is usually recirculated through the cell from a separate tank, such as a drag out recovery rinse.

Electrolytic recovery is typically applied to solutions containing nickel, copper, precious metals, and cadmium. Chromium and aluminum are poor candidates for electrolytic recovery. Drag out recovery rinses and ion exchange regenerant are common solutions that are processed using electrolytic recovery. Some solutions require pH adjustment prior to electrolytic recovery. Acidic, metal rich, cation regenerant is an excellent candidate stream for electrolytic recovery, and is often electrolytically recovered without adjustment. In some cases, when the target concentration is reached, the wastestream is reused as cation regenerant.

Evaporation Evaporation is a common chemical recovery technology. There are two basic types of evaporators: atmospheric and vacuum. Atmospheric evaporators, the more prevalent type, are relatively inexpensive to purchase and easy to operate. Vacuum evaporators are mechanically more sophisticated and are more energy efficient. Vacuum evaporators are typically used when evaporation rates greater than 50 to 70 gallons/ hour are required. Additionally, with vacuum evaporators, evaporated water can be recovered as a condensate and reused on site.

A disadvantage of evaporation based recovery is that all drag out, including unwanted components, are returned and accumulate in the process bath. For this reason, deionized water is preferred as rinse water to prevent the introduction of water contaminants in the process bath.

Flow Restrictor Flow restrictors prevent the flow in a pipe from exceeding a predetermined volume. They are commonly installed on a rinse tank s water inlet. These devices contain an elastomer washer that flexes under pressure to maintain a constant water flow regardless of pressure. Flow restrictors can maintain a wide range of flow rates, from less than 0.1 gal/ min to more than 10 gal/ min.

As a stand alone device, a flow restrictor provides a constant water flow. As such, for intermittent rinsing operations, a flow restrictor does not coordinate the rinse flow with drag out introduction. Precise control with intermittent operations typically requires a combination of flow restrictors and rinse timers. However, for continuous rinsing ( e. g., continuous electroplating machines), flow restrictors may be adequate for good water control.

Fog or Spray Rinse Over Tank Fog or spray rinsing is performed over a process bath to recover drag out. Draining over a process bath can be greatly enhanced by spray or fog rinsing, which dilutes and lowers the viscosity of the film of process fluid clinging to the parts. This method of drag out recovery is only possible if the evaporation rate of the process fluid is moderate to high.

D 6 Appendix D  Pollution Prevention and Water Conservation Practices Table D 2 ( Continued)

Practice or Technology Description Good Tank Design Rinse tanks should be designed to remove the drag out layer from the part and cause it to rapidly and thoroughly mix with the rinse water. Common elements of good tank design are positioning the inlet and outlet at opposite ends of the tank, using air or other agitation, using a flow distributor, and using the minimum size tank possible.

Ion Exchange Ion exchange is a reversible chemical reaction that exchanges ions in a feed stream for ions of like charge on the surface of an ion exchange resin. Resins are broadly divided into cationic or anionic types. Typical cation resins exchange H+ for other cations, while anion resins exchange OH  for other anions.

In practice, a feed stream is passed through a vessel, referred to as a column, which holds the resin. The feed stream is typically dilute rinse water. The exchange process proceeds until the capacity of the resin is reached ( i. e., an exchange has occurred at all the resin facilities). A regenerant solution is then passed through the column. For cation resins, the regenerant is an acid, and the H+ ions replace the cations captured from the feed stream. For anion resins, the regenerant is a base, and OH  ions replace the anions captured from the feed stream. The concentration of feed stream ions is much higher in the regenerant than in the feed stream; therefore, the ion exchange process accomplishes both separation and concentration.

Ion exchange is used for water recycling and/ or metal recovery. For water recycling, cation and anion columns are placed in series. The feed stream is deionized and the product water is reused for rinsing. Often, closed loop rinsing is achieved. The regenerant from the cation column typically contains the metal species, which can be recovered in elemental form via recovery. The anion regenerant is typically discharged to wastewater treatment. When metal recovery is the only objective, a single or double cation column unit containing selective resin is used. These resins attract divalent cations while allowing monovalent cations to pass, a process usually referred to as metal scavenging. Water cannot be recycled because contaminants other than the target cations remain in the stream exiting the column.

Long Drip Time Long drip times over the process tank reduce the volume of drag out reaching the rinsing system. Automatic lines can be easily programmed to include optimum drip times. On manual lines, racks are commonly hung on bars over process baths and allowed to drip. Barrels can be rotated over the process bath to enhance drainage. Some surfaces cannot tolerate long exposure to air due to oxidation or staining, and would therefore be unsuitable for extended drip times.

Raising Bath Temperature Bath temperature and viscosity are inversely related. Operating at the highest possible bath temperature lowers viscosity and reduces drag out. Higher bath temperatures also increase evaporation, which facilitates efficient recovery rinsing.

Lowering Bath Concentration Operating at the lowest possible concentration reduces the mass of chemicals in a given volume of drag out. Also, viscosity and concentration are directly related and lower process bath concentration lowers viscosity and reduces drag out volume. Contaminants and other substances that build in concentration over the life of a process bath should be controlled at a low level, if possible.

Part Position on Rack Positioning parts on racks to promote rapid draining includes minimizing the profile of the parts emerging from the bath, tilting and inverting cup shaped parts, and avoiding placement of parts directly atop one another.

D 7 Appendix D  Pollution Prevention and Water Conservation Practices Table D 2 ( Continued)

Practice or Technology Description Slow Part Withdrawal The faster a part is removed from a process bath, the thicker the layer of fluid clinging to the part will be. A slower withdrawal rate reduces the thickness of the fluid layer and reduces drag out. Generally, this method of drag out reduction can only be practiced on automatic lines where the withdrawal velocity can be programmed.

Reverse Osmosis Reverse osmosis is a membrane separation technology used for chemical recovery. The feed stream, usually relatively dilute rinse water or wastewater, is pumped to the surface of the reverse osmosis membrane at pressures of 400 to 1,000 psig. The membrane separates the feed stream into a reject stream and a permeate. The reject stream, containing most of the dissolved solids in the feed stream, is deflected from the membrane while the permeate passes through. Reverse osmosis membranes reject more than 99% of multivalent ions and 90% to 96% of monovalent ions, in addition to organic pollutants and nonionic dissolved solids. The permeate stream is usually of sufficient quality to be recycled as rinse water, despite the small percentage of monovalent ions ( commonly potassium, sodium and chloride) that pass through the membrane.

A sufficiently concentrated reject stream can be returned directly to the process bath. The reject stream concentration can be increased by recycling the stream through the unit more than once or by increasing the feed pressure. In multiple stage units containing more than one membrane chamber, the reject stream from the first chamber is routed to the second, and so on. The combined reject streams from multistage units may, in some cases, have high enough concentrations to be returned directly to the bath.

Timer Rinse Controller Rinse timers are electronic devices that control a solenoid valve. The timer usually consists of a button that, when pressed, opens the valve for a predetermined length of time, usually from 1 to 99 minutes. When the valve is open, make up water is allowed to flow into a given tank. After the time period has expired, the valve is automatically shut. The timer may be activated either manually by the operator or automatically by the action of racks or hoists.

Most rinse systems that are used intermittently benefit from the installation of a rinse timer, as operator error is eliminated. Rinse timers installed in conjunction with flow restrictors can provide precise control when the incoming water pressure may rise and fall. Rinse timers are less effective in continuous or nearly continuous rinse operations ( e. g., continuous electroplating machines).

Wetting Agents Wetting agents or surfactants may be added to some process baths to reduce viscosity and surface tension, thereby significantly reducing drag out.

Source: MP& M Site Visits, MP& M Surveys, Technical Literature.

D 8 Appendix D  Pollution Prevention and Water Conservation Practices D. 1.1 Drag Out Reduction and Drag Out Recovery The quantity of water needed for good rinsing for a given system is proportional to the quantity of drag out from a process bath. Facilities can implement various methods that minimize the rate of drag out ( measured as gallons per square foot of part surface area) and/ or they can implement direct drag out recovery. The drag out rate for an individual process operation ( e. g., cleaning or plating) depends on numerous factors, including process type, shape of parts processed, production equipment, and processing procedures, which include human factors. Of these factors, the shape of the parts and the type of device used to move the parts ( e. g., racks, baskets, barrels) usually have the greatest influence on drag out rates. Tables D 3 and D 4 present drag out rate estimates from two sources in the literature for various shaped parts.

Table D 3 Average Drag Out Losses  from Soderberg s Work Nature of Work Drainage Drag Out Rate ( gal/ 1,000 ft2)

Vertical Well drained 0.4 Poorly drained 2 Very poorly drained 4 Horizontal Well drained 0.8 Very poorly drained 10 Cup Shapes Well drained 8 Very poorly drained 24 Source: Reference 4.

D 9 Appendix D  Pollution Prevention and Water Conservation Practices Table D 4 Average Drag Out Losses  from Hogaboom s Work Electroplating Solution Type Drag Out Rate ( gal/ 1,000 ft2)

Flat Surfaces Contoured Surfaces Brass 0.95 3.3 Cadmium 1 3.1 Chromium ( 33 oz/ gal) 1.18 3 Chromium ( 53 oz/ gal) a 4.53 11.9 Copper cyanide 0.91 3.2 Watts nickel 1 3.8 Silver 1.2 3.2 Stannate tin 0.83 1.6 Acid zinc 1.3 3.5 Cyanide zinc 1.2 3.8 Source: Reference 4. a Increased viscosity, caused by an increase in concentration, can increase the drag out volume approximately three times with less than double the concentration increase.

Several factors other than shape, some of which are interrelated, influence the drag out rate for a given process and part. Table D 5 lists these and other key factors and describes their impact on drag out rates. Also listed are examples of water conservation practices that reduce the generation of drag out, and the major restrictions that are associated with these practices. Table D 6 shows the effect of altering the withdrawal rate and drain time.

Soderberg s data indicate that the shape of the part has a significant influence on drag out rate. Cup shaped parts, including intricately designed parts with internal surfaces, can generate five or more times the drag out than flat surfaced parts with the same surface area. Hogaboom s data show a similar trend for flat versus contoured surfaces. These data also show that the type and concentration of the electroplating solution influence the drag out rate. For example, some solutions, such as stannate tin, drain effectively, while others, such as concentrated chromium electroplating solutions ( 53 ounces per gallon ( oz/ gal) drain poorly. As to the type of device used to move parts, barrels ( used to hold fasteners or other small parts that cannot be practically held by racks) generate more drag out than racks, because of the surface area of the barrel and its tendency to hold the solution.

D 10 Appendix D  Pollution Prevention and Water Conservation Practices D 11 Table D 5 Factors Affecting Drag Out Factor Affecting Drag Out Impact on Drag out Potential Pollution Prevention and Water Conservation Practices Restrictions Bath Concentration Concentration and drag out are directly related. Operate at lowest concentration possible. Remove all contaminants promptly. Concentration range limited by process.

Bath Temperature Higher temperatures lower drag out by lowering viscosity. Operate at highest possible temperature. Temperature range limited by process.

Bath Viscosity High viscosity raises drag out by increasing the thickness of the fluid layer clinging to the part. Operate at highest temperature and lowest concentration possible. Add wetting agent. Concentration and temperature ranges limited by process. Wetting agent must be compatible.

Part Configuration Cup shapes result in 8 20 times the drag out volume of flat shapes. Drain holes can be added to many cup shaped parts to improve drainage of drag out. Functionality of parts may restrict use of drain holes or other changes to part configuration.

Part Orientation Orientation on rack can be optimized to minimized drag out. Keep records of optimal orientations. Train operators. None.

Withdrawal Rate Doubling speed of withdrawal results in a fourfold increase in drag out volume. Program automatic equipment for slow withdrawal. Impossible to consistently practice without automation.

Drain Time Long drain times and barrel rotations greatly reduce drag out. Program automatic equipment for long drain times. Impossible or difficult to consistently practice without automation. Drain time limited by staining or passivation of some coatings.

Rack versus Barrel Barrels produce greater drag out than racks. ( See   Rack/ Barrel Design) Part transport device is dictated by part size.

Rack/ Barrel Design Drag out volume is related to barrel design. Redesign barrels with largest holes possible. Barrel design limited by part sizes and configurations.

Rack/ Barrel Condition Loose rack coating cause reservoirs of fluid to be transported with rack. Maintain a schedule of maintenance and recoating. None.

Operator Awareness Poor operator awareness greatly increases drag out or offsets other practices. Require training programs for operators. None.

Source: MP& M Site Visits, MP& M Surveys, Technical Literature. Appendix D  Pollution Prevention and Water Conservation Practices Table D 6 Effect of Withdrawal Rate and Drain Time on Drag out Ratea Micro Etch Results Withdrawal Rate ( ft/ min) Time of Withdrawal ( seconds) Drain Time ( seconds) Total Time ( seconds) Drag out ( gal/ 1,000 ft2)

Baseline 100 1.7 3.4 5.1 3.13 Slower rate of withdrawal 11 14.9 2.5 17.4 1.73 Intermediate withdrawal rate and longer drain time 40 4.3 12.1 16.4 1.83 Electroless Copper Results Withdrawal Rate ( ft/ min) Time of Withdrawal ( seconds) Drain Time ( seconds) Total Time ( seconds) Drag out ( gal/ 1,000 ft2)