REPLACING MERCURY CONTAINING PRODUCTS AND MERCURY THERMOMETERS IN

REPLACING MERCURY CONTAINING PRODUCTS AND MERCURY THERMOMETERS IN ASTM STANDARDS Technical and Legal Issues Presented by Jim & Deanne Emory Miller & Weber, Inc. Ridgewood, NY June 26, 2007

• Deanne Miller Emory President & Owner of Miller & Weber, Inc. Precision Glass Instruments Ridgewood, NY Chairman, E 20. 05 Liquid-in-Glass Thermometers & Hydrometers Chairman, ASTM E 20 Mercury Project Task Group Secretary, E 20. 04 on Thermocouples Member-at Large, D 02 Committee on Petroleum • James E. Emory, Jr. Judicial Referee and Senior Court Attorney New York State Office of Court Administration Member, E 20 Committee on Temperature Measurement CONTACT US: Deanne. MEmory@aol. com (718) 821 -7110

Abstract At the request of several States, ASTM International has issued a directive to all technical committees to review their standards that reference mercury containing instruments or mercury methods and determine the technical and economic feasibility of replacing them or substituting with non-mercury instruments or methods. A number of States have banned the sale of mercury containing instruments, including ASTM mercury thermometers, making it difficult for users in those States to comply with ASTM standards. In most cases, the instruments in question are the mercury-in-glass thermometers specified in ASTM E 1. These thermometers have long been the gold standard temperature measurement devices in many ASTM standards. In this presentation we will review the ASTM directive, including how to communicate the technical committees’ resolutions to ASTM; technical issues in replacing mercury containing devices with other devices, especially thermometers found in ASTM E 1; legal issues involved with this project, including which States have bans and how the bans differ from State to State. We will leave discussion time at the end of the presentation.

How did this start?

NEWMOA The Northeast Waste Management Officials’ Association based in Boston, Massachusetts found at www. newmoa. org

Member States • • Connecticut Maine Massachusetts New Hampshire New Jersey New York Rhode Island Vermont NEWMOA was established by the Governors of the New England states as an official regional organization to coordinate interstate hazardous and solid waste, and pollution prevention activities and support state waste programs, and was formally recognized by the U. S EPA in 1986.

IMERC • In 2001, NEWMOA established IMERC--the Interstate Mercury Education & Reduction Clearinghouse. • The State- Laws we will discuss first came out of this Clearinghouse. • IMERC States include all of the NEWMOA states and California, Illinois, Minnesota, North Carolina and Washington.

ASTM INITIATIVE

ASTM Involvement • In January 2006, state environmental agencies became aware of Federal and State rules and regulations that require the use of ASTM standards. Many of these standards require the use of mercury in glass (ASTM E 1) thermometers. • States began to lobby ASTM to remove requirement of mercury in their standards.

ASTM Search • In response to the requests, ASTM searched through their standards for references to ASTM E 1, mercury -in-glass thermometers and liquid-in-glass thermometers. • ASTM E 1 is the most referenced standard within ASTM- it is referenced in over 900 standards.

ASTM Response • ASTM Headquarters has requested each technical committee to review standards and determine whether the use of “mercury” or “mercury products” is appropriate; if it can be replaced or supplemented with non-mercury methods or products; if the reference should be removed without replacement of method or product.

ASTM E 20 Mercury Project Task Group • Consists of seven members of ASTM Committee E 20 to help provide technical guidance to the committees affect by this review. • We have technical experts in liquid-in-glass thermometry, resistance thermometry, themocouples, radiation thermometry, thermistors and in calibration and construction. • Guidance document developed for distribution to Subcommittee Chairmen and is available today.

ASTM Committee E 20 on Temperature Measurement Overview of Committee and Committee Standards

Technical Subcommittees • • E 20. 02 E 20. 03 E 20. 04 E 20. 05 • E 20. 06 • E 20. 07 • E 20. 08 Radiation Thermometry Resistance Thermometry Thermocouples Liquid-in-Glass Thermometers and Hydrometers New Thermometers & Techniques Fundamentals Medical Thermometry

ASTM Committee E 20 Temperature Measurement ASTM Subcommittee E 20. 05 Liquid-in-Glass Thermometers and Hydrometers & Thermohydrometers Liquid-in-Glass Thermometers • • • ASTM E 1 “Standard Specification for ASTM Liquid-in-Glass Thermometers” ASTM E 77 “Standard Test Method for Inspection and Verification of Thermometers” ASTM E 2251 “Standard Specification for Liquid-in-Glass ASTM Thermometers with Low. Hazard Precision Liquids” • ASTM E 100 “Standard Specification for ASTM Hydrometers • ASTM E 126 “Standard Test Method for Inspection, Calibration and Verification of Hydrometers • NEW “Standard Specification for ASTM Thermohydrometers using Non-Mercury Liquids” • NEW “Standard Specification for Electronic Thermohydrometers (densitometers) using the Digital Buoyancy Method” • NEW “Standard Test Method for Calibration and Verification of Electronic Thermohydrometers (Densitometers)”

ASTM Committee E 20 Temperature Measurement Other Standards of Interest • Resistance Thermometry E 644 - Standard Test Methods for Testing Industrial Resistance Thermometers. E 1137 - Standard Specification for Industrial Platinum Resistance Thermometers • Thermocouples E 220 - Standard Test Method for Calibration of Thermocouples by Comparison Techniques E 230 - Specification for Temperature- Electromotive Force (EMF) Tables for Standardized Thermocouples • Fundamentals E 563 - Standard Practice for Preparation and Use of an Ice. Point Bath as a Reference Temperature

SUMMARY STATE BANS ON MERCURY-IN-GLASS THERMOMETERS as of June 15, 2007

CALIFORNIA Effective July 1, 2006 A person shall not sell, offer to sell, or distribute for promotional purposes, any of the following new or re-furbished mercuryadded products…. Barometer… flow meter… hydrometer… hygrometer… psychrometer… manometer… pyrometer… thermometer. This does not apply to the sale of a mercury-added product if the use of the product is required under federal law or federal contract specification or if the only mercury-added component in the product is a button cell battery. California Codes Health and Safety Code 25214. 8. 3.

CONNECTICUT Effective July 1, 2004 (add’l req. July 1, 2006) … no person shall offer for sale or distribute for promotional purposes any mercury-added product if the mercury content of the product exceeds 100 mg in the case of fabricated mercury-added products or 50 ppm in the case of formulated mercury added products Manufacturer may apply for an exemption. Connecticut Chapter 446 m Mercury Reduction and Education Sec 221 -617.

INDIANA Effective July 1, 2003 A person may sell or provide a mercury commodity to another person in this state (other than for collecting for recycling) only if: (1) the person selling or providing the mercury commodity provides an MSDS… (2) person selling or providing the mercury commodity requires that the purchaser or recipient will (a) use the mercury only for medical purposes, in dental amalgam, dispose-caps, for training, for research or for manufacturing purposes (b) understands that mercury is toxic, (c) will store and use properly. . (d) will not intentionally place… in solid waste for disposal or in a wastewater disposal system. Indiana IC 13 -20 -17. 5 -5

MAINE Effective July 1, 2006 A person shall not sell or offer to sell or distribute the following mercury-added products: Barometer… flow meter… hydrometer… hygrometer or psychrometer… manometer… pyrometer… thermometer… This section does not apply to the sale of the above products if the use of the product is a federal requirement or if the only mercury-added component in the product is a button cell battery. Manufacturer may apply for an exemption. Maine Title 38, Chapter 16 -B, Section 1661 -C-6

MASSACHUSETTS Effective May 1, 2007 Manufacturers of products to which mercury has been intentionally added and that are sold in the state must establish a system of collecting them at the end of their useful lives, and for recycling their mercury contents. The plan must be approved and certified by the department. Unless the mercury-added product is required under federal law. Massachusetts Chapter 190 of the Acts of 2006, Section 6 J

MICHIGAN Effective January 1, 2003 (Ban includes) all mercury thermometers sold or offered for promotion… …except those (1) required by state or federal statute, regulation, or administrative rule, (2) used for pharmaceutical research purposes. Enforcement shall be done by dept of environmental quality. A person who violates this part is guilty of a misdemeanor punishable by imprisonment of not more than 60 days or a fine of not more than $1, 000. 00, or both, plus the costs of prosecution. Michigan Act 451 of 1994, Sections 324. 17201 & 324. 17202

MINNESOTA Effective January 1, 2002 Includes all mercury thermometers manufactured after June 1, 2002, Except those (1) used for food research and development or processing, (2) are a component of an animal agriculture climate control system or industrial measurement system, until a system is replaced or a non-mercury component is available, (3) used for calibration of othermometers, apparatus or equipment unless a nonmercury calibration standard is approved by NIST and (4) electronic thermometers with button cell batteries. Minnesota Chapter 47 - H. F. No 274

NEBRASKA Effective May 20, 2003 No liquid mercury thermometer containing elemental mercury shall be sold, given away, or otherwise distributed in this state. No exceptions in statute. Nebraska Chapter 28, Section 28 -1349 & 28 -1350 (Laws of 2003, LB 17 Section 3 & 4)

NEW YORK Effective January 1, 2007 (Bans) all mercury-added manometers and hydrometers, except those used to replace a product that is a component in a larger product in use prior to January 1, 2007, or the resale of a manometer or hydrometer manufactured before December 31, 2006. New York Title 21, Section 27 -2107, 6

NEW YORK Effective January 1, 2008 Cannot sell, offer for sale, or distribute mercury-added thermometers if a non-mercury alternative is available. Commission will review this by February 2008 and rule if non-mercury alternatives are available. Excludes mercury-added thermometers that are a component of a larger product in use prior to January 1, 2008 or resale manufactured before January 1, 2008; excludes if the use is a federal requirement. New York Title 21, Section 27 -2107, 8

RHODE ISLAND Effective January 1, 2006 - revise 1/1/07 & 1/1/08 No mercury added product shall be offered for final sale or use or distributed for promotional purposes in the state if the mercury content of product exceeds 1 gram for fabricated products and 250 ppm formulated products. Excludes are lighting for entertainment industry and fluorescent lamps and HID lamps. Manufacturers may apply for exemption. Rhode Island Title 23, Health & Safety, Mercury Reduction & Eductation Act. Chapter 23 -24. 9 -7

VERMONT Effective January 1, 2007 Restricts the sale of thermometers that contain elemental mercury Excludes if it is for a Federal requirement. Also … barometers… flow meters… hygrometers & psychrometers… manometers… hydrometers. Excludes Hygrometers, psychrometers & manometers if replacing into larger device in place before 1/1/07. Exemptions may be granted. Vermont Chapter 164, Section 7105

WASHINGTON Effective January 1, 2006 (Ban) includes all mercury thermometers… except those (1)electronic thermometers with a button cell battery containing mercury (2) used for food research and development or processing including meat, dairy products, and pet food processing, (3) are a component of an animal agriculture climate control system or industrial measurement system, until a system is replaced or a non-mercury component is available, (3) used for calibration of othermometers, apparatus or equipment unless a nonmercury calibration standard is approved by NIST and (4) electronic thermometers with button cell batteries. Washington Chapter 70. 95 M. 050

So, how do we substitute for this?

What about our manual methods?

Thermometer Types • Standard Platinum Resistance Thermometers (SPRTs) (very accurate, but susceptible to shock) 13. 8 K to 962 °C (Calibration uncertainty less than 0. 001 °C *) • Industrial Platinum Resistance Thermometers (IPRTs) – 196 °C to 850 °C (Calibration uncertainty less than 0. 01 °C *) • Thermistors – 10 °C to 100 °C (Calibration uncertainty less than 0. 005 °C *) • Liquid-in-Glass Thermometers – 150 °C to 400 °C (Calibration uncertainty between 0. 02 and 0. 5 °C *) • Thermocouples – 196 ° C to 2100 °C (Calibration uncertainty between 0. 3 and 1 °C *) * U (k=2) Information courtesy of NIST

Digital Thermometers • A digital thermometer is an electronic “box” that converts either resistance or emf of a thermometer to temperature. • Platinum Resistance Thermometers, thermistors and thermocouples in disguise. Pictures courtesy of Fluke/Hart Scientific, ASL and WL Walker Co.

Thermometer Types: Calibration Ranges and Uncertainties Chart used with permission of NIST Thermometry Group

Determine Differences in Scale Error and Uncertainties PRT’s and Thermistors COMPONENT METHOD OF EVALUATION Calibration uncertainty or tolerance Manufacturer or calibration laboratory Alternative sensor drift Manufacturer’s specifications, or customer history Hysteresis of alternative sensor (PRTs only) ASTM Method E 644, implemented by manufacturer or customer Readout uncertainty Manufacturer or independent evaluation Readout drift Manufacturer or independent evaluation Used with permission of the NIST Thermometry Group

Determine Differences in Scale Error and Uncertainties Thermocouple Sensors COMPONENT METHOD OF EVALUATION Calibration uncertainty or tolerance Manufacturer or calibration laboratory Thermocouple drift Results from literature or in situ comparisons (see ASTM MNL 12) Reference junction uncertainty Manufacturer or independent evaluation Readout drift Manufacturer or independent evaluation Used with permission of the NIST Thermometry Group

Additional Constraints • Sensor should be hermetically sealed in stainless steel sheath of outer diameter no larger than the bulb diameter of the E 1 thermometer. • When substituting for a partial immersion thermometer, immerse at least as deep as you would the glass thermometer. A bias may be introduced due to temperature gradients in the ASTM apparatus if the immersion is very different from the glass thermometer. • When substituting for a total immersion thermometer, the center of the alternative sensor should be placed at a depth equal to the center of the liquid-in-glass thermometer. Again, bias may be introduced since PRT can be fixed in place and there may be temperature gradients. • PRTs should be fabricated to ASTM E 1137. • Thermistors should be fabricated to ASTM E 879. • Thermocouples should be fabricated either of soft-insulated wire mounted in stainless-steel sheaths similar to the mountings described in E 879 or E 1137, or of mineral insulated construction in conformance with E 608.

General Issues with Replacing Mercury-in-Glass Thermometers in ASTM Standards

ASTM Total Immersion Liquid-in-Glass Thermometers • Total immersion thermometers, when properly used have immersion depths that vary with temperature. • Some ASTM total immersion thermometers (such as ASTM Calorimetry thermometers) are not manufactured to measure absolute temperature. • ASTM Kinematic Viscosity thermometers have ice points that do not read absolute temperature. • Many ASTM total immersion thermometers (such as distillation and saybolt viscosity thermometers) are used as partial immersion thermometers.

ASTM Distillation Manual Methods ASTM 8 C vs Electronic Thermometer Difference in Readings 50. 0 °C ASTM 8 C Reading 49. 9 °C 100. 0 150. 0 200. 0 250. 0 300. 0 350. 0 400. 0 99. 1 °C 147. 5 °C 195. 2 °C 242. 0 °C 288. 0 °C 333. 3 °C 377. 8 °C -0. 9 °C -2. 5 °C -4. 8 °C -8. 0 °C -12. 0 °C -16. 7 °C -22. 2 °C °C -0. 1 °C

ASTM Partial Immersion Mercury-in-Glass Thermometers • Many ASTM partial immersion mercury-in-glass thermometers have “artificially” high or low emergent stem temperatures. • Study of differences in readings of mercury-inglass thermometer and substitute thermometer (whether liquid-in-glass or electronic must be made before relying on the substitute thermometer. • Special care must be taken when substituting in timed tests (ie flashpoint). Rate of rise and lag time must be accounted for.

Typical Alternative Liquids typically available in thermometers • Toluene (ASTM 6 C & ASTM 114 C) • Kerosene • Mineral Spirits • Silicones • Citrus Oils • Iso. Amyl Benzoate Properties of Typical Alternative Liquids as Compared to Mercury Less hazardous than mercury Reaction time descending up to fifteen minutes. Repeatability less precise than mercury

Typical non-mercury thermometers do not have tolerance, repeatability or response time adequate for use in ASTM standards. WHY?

Behaviors of Traditional Liquids in Glass Capillaries

Desirable Behaviors of Mercury as a Thermometric Liquid • Expands Uniformly • Wide useable range (-39 to 500 °C) • Reaction time three minutes • Repeatable measurement capability

ASTM E 2251 “Standard Specification for Liquid-in-Glass ASTM Thermometers with Low-Hazard Precision Liquids” • Written by the NIST Thermometry group and members of ASTM E 20. 05 based on the research presented at the 8 th International Temperature Symposium in October 2002. • Accepted by ASTM Committee E 20 in November 2002. • Published by ASTM in February 2003.

“Preliminary Results of a New Type of Non-Hazardous Liquid-Filled Precision Glass Thermometer” • Research presented at the 8 th International Temperature Symposium in Chicago, Illinois October 2002. • Research published by the AIP in the Conference Proceedings. CP 684, Temperature: Its Measurement and Control in Science and Industry, Volume 7. Edited by Dean C. Ripple.

PROPERTIES REQUIRED OF ASTM E 2251 THERMOMETERS • Liquid column will ascend or descend with change of temperature so that top of liquid column reaches final position within 3 minutes of attaining temperature to be measured. • Liquid column will descend through a contraction chamber or ice point chamber and will reach final position within 3 minutes of attaining temperature to be measured. • Liquid is biodegradable • Liquid is non-toxic in thermometer quantities (per 49 CFR 1910. 1200) • Liquid is non-hazardous (per EPA Regulations) • Thermometer will give repeatable results similar to those expected of a mercury thermometer • Thermometer will give reproducible results similar to those expected of a mercury thermometer

Behaviors of Traditional Liquids in Glass Capillaries

Current available E 2251 Thermometers • Thermometers currently being manufactured to ASTM E 2251 show no meniscus under 5 X magnification. • Future generations now in R&D may show cohesive forces greater than adhesive forces as with mercury.

Thermometers currently available and approved in ASTM E 2251 • • ASTM S 12 C &F ASTM S 56 C & F ASTM S 59 C & F ASTM S 62 C & F thru ASTM S 67 C & F ASTM S 91 C ASTM S 116 C ASTM S 117 C ASTM S 120 C Density Wide Range Bomb Calorimetry Tank Precision Distillation Bomb Calorimetry Kinematic Viscosity

So, how do we substitute for this?

• Subcommittee E 20. 05 is currently working on a new standard for thermohydrometers with non-mercury liquids. • The draft standard, as currently written has the maximum permissible error of thermohydrometer thermometers at approximately double the maximum permissible error of the mercury filled thermometers in the ASTM E 100

Glass Hydrometer Method If you are using a hydrometer method, the best alternative we have today is a plain form hydrometer with an ASTM E 2251 ASTM S 12 C or ASTM S 12 F density thermometer in the cylinder to measure the temperature.

Digital Densitometers using the digital buoyancy method • Newly available in the United States, these instruments can be used as direct replacements for glass hydrometers, glass thermohydrometers and they can do direct reading of density directly in the storage unit or tank car. • They are durable, simple to use, and unlike U-tube densitometers, easy to clean.

What to do next? • Decide whether you mercury-in-glass thermometer is a “gold standard”. If so, give rationale for leaving the method or instrument as a requirement to the standard. • If you are going to allow substitutes, decide which types will be adequate for use in your standard. • If necessary, do studies to identify whether your precision and bias statements will be affected. • If necessary, have new thermometers that meet your subcommittee needs added to ASTM E 2251.

Finish work for ASTM Headquarters • Ballot changes to standard- including the addition of a mercury caveat, if appropriate. • Subcommittee respond back to ASTM on action to be taken in each standard identified in “the search”. This response can go to your staff manager.