Technical Analysis

Hot topics in metalworking fluids

Greg Foltz, Eugene White, John Howell, Fred Passman, Neil Canter, Mike Pearce & John Burke | TLT Technical Analysis May 2013

Our expert panel talks about the latest product and regulatory challenges impacting the metalworking fluid and lubricant industries.

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Editor’s Note: The metalworking fluid industry continues to be at the forefront of regulatory activity—either directly through actions impacting the products themselves, or indirectly as key raw materials used in the formulations are being affected.

In 2010, the STLE MWF Education and Training Subcommittee selected several current MWF hot topics for presentation in a one-day education course at the STLE 2011 Annual Meeting in Atlanta. The course was so well-attended and popular, that a half-day panel session devoted to these hot topics was also held at the STLE 2012 Annual Meeting in St. Louis.

Due to the importance of these topics and the interest in them, this information is being made available to a much wider audience in TLT. Another MWF hot topics session is being presented at this month’s STLE Annual Meeting in Detroit.

In this article, we have brought together the following original presenters from the course, as well as the panel session, to provide updates on various areas affecting the MWFs and lubricant industries:

• Dr. Eugene White, EHS manager, Milacron LLC/CIMCOOL® Global Industrial Fluids (The Globally Harmonized Standard of Classification and Labeling of Chemicals (GHS))
• Dr. John Howell, vice president, GHS Resources, Inc. (Hazard Communication Standard (HCS))
• Dr. Fred Passman, president, Biodeterioration Control Associates, Inc. (formaldehyde-condensate microbicides)
• Dr. Neil Canter, owner, Chemical Solutions (chlorinated paraffins)
• Mike Pearce, senior sales representative and formulator, W.S. Dodge Oil Co. (AQMD Rule 1144)
• John Burke, global director of engineering, Houghton International Inc. (ASTM E1868-10 TGA method for VOC determination)

GHS will have a major impact on product labels in terms of the language and pictograms now required. It will also affect safety data sheets (SDSs) in terms of trade secrets, mixture reporting and hazard determination. OSHA has mandated that this be in place in the U.S. by June 1, 2015. This issue will impact everyone in the lubricant industry—not just MWFs.

Chlorinated paraffins are key ingredients to many metal-removal fluids and are critical ingredients in many forming fluids. Their availability and regulatory status is important to many formulators. The same goes for the biocides used in MWFs, especially the formaldehyde condensates, many of which are coming up for reregistration. Rule 1144 defines regulations for the use of VOC containing MWFs in the South Coast Air Quality Management District (AQMD) of California. It is now in place and is being enforced. A new ASTM method (E1868-10) was developed in conjunction with Rule 1144 and is used for measuring the VOC of MWFs.

These are all very timely and pertinent topics, which will have a major impact on businesses in terms of financial resources required, potential product reformulations and the ability to maintain regulatory compliance.

Greg Foltz
Chair, STLE MWF Education and Training Subcommittee

MEET THE PRESENTERS

Greg Foltz, CMFS, is the engineering and development manager for CIMCOOL Industrial Products LLC in Cincinnati. He has been involved with MWFs since 1978. He holds STLE’s Certified Metalworking Fluids™ (CMFS) certification and is responsible for the development of CIMCOOL metalworking products. Greg is a past president of ILMA and is the chair of STLE’s MWF Education and Training Subcommittee. You can reach him at greg_j_foltz@cimcool.com.

Dr. Eugene White, CMFS, is the environmental, health and safety manager for Milacron LLC/CIMCOOL® Global Industrial Fluids in Cincinnati. Prior to joining Milacron, he was a scientist at the Centers for Disease Control and Prevention (CDC)/National Institute for Occupational Safety and Health (NIOSH) where he conducted research on MWF occupational exposures. Eugene has published extensively in peer-review journals and was a contributor to the second edition of the textbook, Metalworking Fluids (Edited by Jerry Byers), including a chapter entitled “Regulatory Aspects of Metalworking Fluids.” You can reach him at eugene_m_white@cimcool.com.

Dr. John Howell, CMFS, is vice president of GHS Resources, Inc., in Bonita Springs, Fla., which specializes in preparation of GHS-compliant SDSs for the lubricant industry. John has over 42 years of experience in metal-finishing and metalworking technology, and in safety, health and environmental affairs. Previously, he worked for 23 years at Castrol Industrial North America and predecessor companies, and several years with D.A. Stuart and Primagy Consultants. You can reach him at jhowell@ghsresources.com.

Dr. Fred Passman, CMFS, is president of Princeton, N.J.-based Biodeterioration Control Associates, Inc., an industrial microbiology consulting firm. Fred has been investigating the microbiology of MWFs since 1981. He has written more than 40 papers and book chapters on fuel, lubricant and MWF microbiology and has twice received the STLE Wilbur Deutch Memorial Award (1997 and 2011). In 2012 Fred was presented with STLE’s P.M. Ku Award. He has chaired STLE’s Education Course Committee, Education Committee, MWF Education and Training Committee, Metalworking Fluid Certification Steering Committee, Certification Board, and currently chairs the Education and Certification Harmonization Executive Committee. Fred is chair of ASTM E.34.50 on the Health & Safety of Metalworking Fluids and ASTM D.02.14 Fuel Microbiology Working Group and is vice chair of ASTM D.02.14 Fuel Stability and Cleanliness and E.34 Industrial Health and Safety. You can reach him at fredp@biodeterioration-control.com.

Dr. Neil Canter, CMFS, is owner of Chemical Solutions in Willow Grove, Pa. He specializes in commercial development, marketing, product development and regulatory support for the MWF industry, where he has over 25 years of experience. Previously, he worked for Stepan Co. and Mayco. Neil is a member of ACS, SAE and STLE and also serves as a TLT contributing editor and is the chair of STLE’s MWF Steering Committee and a member of the STLE Education Committee. You can reach him at neilcanter@comcast.net.

Mike Pearce, CMFS, is the senior sales representative and formulator for W.S. Dodge Oil Co. in Maywood, Calif. He has been working in the field of metalworking and machinery lubrication for 38 years. For the past five years, Mike has helped lead the negotiations with the South Coast Air Quality Management District over Rule 1144. Mike is an active member of STLE, ILMA and ASTM and serves on STLE’s MWF Education and Training Subcommittee. You can reach him at mikep@wsdodgeoil.com.

John Burke, CMFS, is the global director of engineering services for Houghton International Inc., in Valley Forge, Pa. John has 40 years of experience in the metalworking industry, and has five U.S. patents. John has been an instructor for STLE’s MWF education course for the past 20 years. He is an STLE Fellow and recipient of the P.M. Ku Award (2006). John received an award from President George Bush at the White House in 1991 for advances in waste minimization. You can reach him at jburke@houghtonintl.com.

GHS
On May 25, 2012, a major revision of OSHA’s almost three-decades old Hazard Communication Standard (HCS; 29 CFR 1910.1200) officially came into alignment with the UN’s’ Globally Harmonized System of Classification and Labeling of Chemicals (GHS) (1).

OSHA estimates that the revamped HCS would prevent 500 occupational injuries and 43 fatalities annually. Furthermore, the standard could result in savings to U.S. businesses of more than $475 million in productivity improvements (2). As a result of HazCom 2012, there has been a paradigm shift from The Right to Know to The Right to Understand, which will impact over 40 million workers and 5 million workplaces that comprise approximately 90,000 producers of hazardous chemicals that employ three million workers (3). (For more information about the GHS regulations, check out the March 2013 TLT, available digitally at www.stle.org).

According to former U.S. Secretary of Labor Hilda Solis, “Revising OSHA’s Hazard Communication Standard will improve the quality and consistency of hazards information, making it safer for workers to do their jobs and easier for employers to stay competitive (4).” GHS is expected to decrease barriers to international trade and commerce.

Significant HazCom modifications were made in the following areas:

1. Hazard Classification (Appendix A To §1910.1200). Manufacturers and importers of chemical products must determine the health and physical hazards of their products according to specific criteria. Classification of a chemical mixture (two or more substances that do not react) is facilitated by using test data. However, when no data are available, bridging principles can be applied by using test data for mixture constituents to estimate hazards. If bridging principles are not applicable, a mixture can be classified according to the weight of evidence available.

2. Labels (Appendix C to §1910.1200). Prior to HazCom 2012, the wide variety of labels in the marketplace often led to misunderstandings and confusion about product hazards. The new standard requires the following information on labels for all shipped containers:

• Product identifier (Appendix C.1 to §1910.1200)
“The labels on shipped containers shall also include the name, address and telephone number of the chemical manufacturer, importer or responsible party.”

• Signal word (Appendix C.2 to §1910.1200)
o “Danger” – more severe hazard
o “Warning” – less severe hazard

• Pictogram (Appendix C.2.3.2 to §1910.1200)
o The appropriate black hazard symbol shall be on a white background within a red square frame set on a point (diamond). Example (exclamation mark):

• Hazard Statement Text (Appendix C.2.2 to §1910.1200)
Describes particular hazard class, category and degree of hazard.

• Precautionary Statement (Appendix C.2.4 to §1910.1200)
o Recommendation to prevent/reduce exposures to a hazardous chemical.

3. Safety Data Sheet (SDS) (Appendix D to §1910.1200 (g))

There is now a proscribed 16-section format:

Section 1. Identification
Section 2. Hazard(s) identification
Section 3. Composition/information on ingredients
Section 4. First-aid measures
Section 5. Fire-fighting measures
Section 6. Accidental release measures
Section 7. Handling and storage
Section 8. Exposure controls/personal protection
Section 9. Physical and chemical properties
Section 10. Stability and reactivity
Section 11. Toxicological information
Section 12. Ecological information*
Section 13. Disposal considerations*
Section 14. Transport information*
Section 15. Regulatory information*
Section 16. Other information, including date of preparation or last revision.
*May be included, but not required; not under OSHA auspices.

As a means of improving the readability of the new HCS, many technical details of the document were moved to appendices:

Appendix A to §1910.1200 – Health Hazard Criteria (Mandatory)
Appendix B to §1910.1200 – Physical Hazard Criteria (Mandatory)
Appendix C to §1910.1200 – Allocation of Label Elements (Mandatory)
Appendix D to §1910.1200 – Safety Data Sheets (Mandatory)
Appendix E to §1910.1200 – Definition of “Trade Secret” (Mandatory)
Appendix F to §1910.1200 – Guidance for Hazard Classifications Re: Carcinogenicity (Non-Mandatory).

Phase-in activities for HazCom 2012 will occur over the next four years. Table 1 shows this timeline.

Table 1. HazCom 2012 Compliance Dates (5)

*This date coincides with the EU implementation date for classification of mixtures.

OSHA’s Website provides comprehensive information about HazCom 2012 (6).

HCS
HCS 2012, as OSHA now refers to the major modification of the Hazard Communication Standard (HCS), brings with it significant changes that affect lubricant formulators and users alike. Two areas of most significant change are in the area of trade secrets and the change in approach from hazard determination to hazard classification.

In HCS 1994, as OSHA refers to the previous version of the HCS, only hazardous ingredients (those which had an OSHA PEL or ACGIH TLV) needed to be disclosed on a label or material safety data sheet (MSDS). Importantly, concentration ranges, e.g., 1%-5%, were used rather than a component’s specific concentration. And withholding disclosure of the specific identity or concentration of a component using the trade secret provisions of HCS 1994 were most often not needed. In fact, so-called “full disclosure” MSDSs, i.e., MSDSs listing all ingredients present at 1% or more, were often also created, but were generally available (except for major automotive customers) only to those end-users who signed a confidentiality agreement.

No more with HCS 2012. Here is the before and after text of 29 Code of Federal Regulations (CFR), 1910.1200 (i): (new text underlined; deleted text struck through):

(i) Trade secrets.
(1.) The chemical manufacturer, importer, or employer may withhold the specific chemical identity, including the chemical name, other specific identification of a hazardous chemical, or the exact percentage (concentration) of the substance in a mixture, from the ~~material safety data sheet~~ safety data sheet, provided that:
(i)The claim that the information withheld is a trade secret can be supported;
(ii) Information contained in the ~~material safety data sheet~~ safety data sheet concerning the properties and effects of the hazardous chemical is disclosed;
(iii) The ~~material safety data sheet~~ safety data sheet indicates that the specific chemical identity and/or percentage of composition is being withheld as a trade secret; and,
(iv) The specific chemical identity and percentage is made available to health professionals, employees, and designated representatives in accordance with the applicable provisions of this paragraph (i).

What is the impact of this change? It means that unless every SDS has a statement that claims a trade secret for the specific percentage of all chemicals, every ingredient/raw material must be listed with its specific concentration. Lubricant manufacturers must now ascertain how to handle potential disclosure of fluid composition (what was previously contained in so-called “full disclosure” MSDSs) as that level of detail must now be supplied to every end-user. If a lubricant manufacturer claims trade secret status, every ingredient must be revealed with percentages ranges, not specific percentages.

An even greater change in HCS 2012 comes from the new hazard classification process, adapted from the UN’s Globally Harmonized System of Classification and Labeling of Chemicals. Here is the before and after text of 29 CFR 1910.1200 (d)(1) and (d)(2):

(d) Hazard ~~determination~~ classification.
(d)(1) Chemical manufacturers and importers shall evaluate chemicals produced in their workplaces or imported by them to classify the chemicals in accordance with this section. ~~determine if they are hazardous~~ For each chemical, the chemical manufacturer or importer shall determine the hazard classes, and where appropriate, the category of each class that apply to the chemical being classified. Employers are not required to classify ~~evaluate~~ chemicals unless they choose not to rely on the classification ~~evaluation~~ performed by the chemical manufacturer or importer for the chemical to satisfy this requirement.

(d)(2) Chemical manufacturers, importers or employers classifying ~~evaluating~~ chemicals shall identify and consider the full range of available scientific literature and other evidence concerning the potential ~~such~~ hazards. There is no requirement to test the chemical to determine how to classify its hazards. For health hazards, evidence which is statistically significant and which is based on at least one positive study conducted in accordance with established scientific principles is considered to be sufficient to establish a hazardous effect if the results of the study meet the definitions of health hazards in this section. Appendix A to §1910.1200 shall be consulted for classification of ~~the scope of~~ health hazards ~~covered~~, and Appendix B to §1910.1200 shall be consulted for the classification of physical hazards ~~criteria to be followed with respect to the completeness of the evaluation, and the data to be reported~~.

The impact of this change from determination to classification is enormous. OSHA requires formulators to now use a tiered approach to classification of mixtures, beginning with using test data if available and, if not, using defined bridging principles if test data is available for a similar formulation. If data is not available, then formulators must estimate hazards based on known ingredient information.

The classification rules for mixtures in Appendix A are complex. For example, to ascertain the skin or eye irritation/corrosion potential of a formulation, formulators must now use several algorithms comparing the hazard classifications of components to preset criteria. Depending on the classification of the formulation, preset label phrases and pictograms (from Appendix C) must be used.

With HCS 2012, lubricant formulators and users alike must quickly learn a new approach to hazard communication.

FORMALDEHYDE-CONDENSATE MICROBICIDES
Formaldehyde-condensate (F-C) microbicides are antimicrobial pesticides that are produced by the reaction of formaldehyde with one or other organic molecules. For example, to produce a molecule of Hexahydro- 1,3,5-tris(2-hydroxyethyl)-s-triazine (the triazine that is most commonly used in MWFs); for purposes of this discussion, we’ll use triazine to refer to Hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine), one reacts three molecules of formaldehyde with one molecule of monoethanolamine (MEA). There are currently 13 F-C products that are approved by the U.S. EPA for use as MWF microbicides, as shown in Table 2.

Table 2. Formaldehyde-condensate microbicides approved by the U.S. EPA for use in MWFs.

REGULATORY ENVIRONMENT
The U.S. EPA’s Office of Pesticide Programs (OPP) provides oversight for pesticide registration and regulatory compliance in accordance with 40 CFR 159, etc., the Federal Insecticide, Fungicide and Rodenticide Act, in the U.S. In Canada, the Pest Management Regulatory Agency (PMRA) fulfills a comparable function in accordance with Health Canada’s Pest Control Products Act. The Biocidal Products Directive (BPD) is similar to the two North American regulations governing pesticide use. This report will focus primarily on what has been happening within the U.S.

In 2009, the International Agency for Research on Cancer (IARC) reclassified formaldehyde from Group 2A (suspect carcinogen) to Group 1 (known carcinogen). In May 2010, the National Center for Environmental Assessment (NCEA) released a proposed new Integrated Risk Information System (IRIS) report on formaldehyde. The draft was forwarded to the National Academy of Science for review and comment. The draft IRIS report classified formaldehyde as a known human carcinogen. Also in 2010, the National Toxicology Program (NTP) recommended that formaldehyde be classified as known to be a human carcinogen.

OPP issued a Reregistration Eligibility Document (RED) for triazine in June 2008, and in February 2009 notified triazine manufacturers that the agency planned to use the IRIS assessment as the basis for new triazine dose restrictions. This notification was followed with a data call-in in April 2010. During subsequent discussions with industry stakeholders, OPP requested that triazine producers change their product labels to list a maximum permissible end-use concentration of 500 ppm (currently the permissible use range is 250 ppm to 2,500 ppm). OPP’s objective was to balance exposure risk with what they considered to be a sufficient dose.

Their understanding of what constituted a sufficient dose was based on a misunderstanding of conclusions drawn by Linnainmaa and her co-workers’ (Linnainmaa, et al. 2003) control of workers’ exposure to airborne endotoxins and formaldehyde during the use of MWFs (AIHA J 64 (4), pp. 496-500). The authors had actually concluded that >500 ppm triazine was needed to control workers’ exposure to endotoxin.

After additional meetings between industry stakeholders and OPP officials, the OPP had agreed to table any changes to triazine labels until the 2010 IRIS report had been approved. Once that happens (probably sometime between December 2012 and June 2013) OPP will issue a new Reregistration Eligibility Document (RED) for triazine. This is likely to be published in 2014. In the meantime, following OPP’s lead, Canada’s PMRA had planned to apply similar restrictions on triazine labels. In June, days before the new label requirements were to have gone into effect, PMRA agreed to hold that requirement in abeyance until the IRIS had been approved. This means that in North America, changes to maximum permissible dose levels of triazine in MWF will not happen for at least another year. Although the initial focus has been on triazine, it’s generally recognized that OPP will ultimately apply similar restrictions to the use of all of the other F-C microbicides.

MARKET IMPLICATIONS
Currently, F-C products account for approximately 80% of MWF microbicide use (by volume). Typically used at 1,000 ppm to 1,500 ppm in end-use diluted MWF, F-C products are relatively inexpensive on both a price-per-pound ($1.50 to $6.00, depending on product) and cost-totreat basis. Moreover, although no microbicide works equally well in all MWF formulations and applications, as a group, F-C products tend to work well in a much broader range of MWF products than do any non-FC microbicides. This means that protecting MWF from biodeterioration is likely to become more expensive and more technically challenging.

One industry response has been to move towards so-called bioresistant, biocide- free MWF. This could create a whole new set of problems if these formulations simply contain unregistered microbicides.

CHLORINATED PARAFFINS
Chlorinated paraffins have been under regulatory scrutiny over the past 30 years. They remain as the most cost-effective extreme pressure agent used by MWF formulators.

Chlorinated paraffins are organized into the following three classes based on carbon chain length: short chain (C10-13 known as SCCPs), medium chain (C14-17 known as MCCPs) and long chain (C18-30 known as LCCPs). Each of these classes is further segmented based on chlorine content, as shown in Table 3.

Table 3. Chlorinated Paraffin Classes

In 1985, a study from the U.S. National Toxicological Program (NTP) provided evidence for carcinogenic effects with male mice treated with the C23, 43% chlorinated paraffin. In addition, NTP found that the C12, 60% chlorinated paraffin was also a suspect carcinogen.

EPA reviewed the results and found that the LCCPs should not be considered as suspect carcinogens. In 1994 EPA moved to subject SCCPs to Toxic Release Inventory reporting and be listed under SARA Title III Section 313. This regulation prompted much of the MWF industry to move to MCCPs.

Other regulatory bodies have also placed warnings on the use of SCCPs. Canada’s CEPA classified SCCPs as toxic in 1993. The European Union (EU) classified SCCPs as a Category 3 Carcinogen in 2004 followed by Australia and Japan.

In 2005, the EU required that MCCPs be labeled as toxic to aquatic organisms.

Environment Canada initiated a review of chlorinated paraffins in 2002 by requiring suppliers to report on the amount of chlorinated paraffin handled in Canada in 2001 and 2002. In June 2005, Environment Canada recommended that all chlorinated paraffins be virtually eliminated.

A final risk assessment in August 2008 concluded that all chlorinated paraffins pose a risk to human health and/or the environment. In September 2009, Environment Canada proposed to place all chlorinated paraffins up to C20 on Canada’s Virtual Elimination List.

In December 2009, EPA developed an action plan for chlorinated paraffins based on its concern that specific chlorinated paraffins from the three classes are not on the U.S. TSCA Inventory, which is needed for them to be used commercially.

EPA claimed that there are discrepancies between the actual chlorinated paraffins used in the U.S. and those listed on the TSCA Inventory. The current chlorinated paraffin suppliers were requested to file premanufacturing notifications (PMNs) for CAS numbers, better reflecting the actual chlorinated paraffins used in industry but not listed on the TSCA Inventory. Further information on the action plan can be found here.

The source of EPA’s concern can be found in Table 4 where the CAS numbers currently on TSCA are very general, while the CAS numbers on the Canada Domestic Substances List (DSL) are comparable to the three classes of chlorinated paraffins. It is assumed that EPA would like the CAS numbers on the DSL list to be placed on the TSCA Inventory.

Table 4. Difference in descriptions between CAS numbers on TSCA and CAS numbers on Canada’s DSL.

RECENT REGULATORY ACTIVITY
Environment Canada proposed to place SCCPs on the list of prohibited substances in July 2011. Two months later, Environment Canada decided to take no further action on LCCPs with carbon chain lengths greater than C20. At the same time, Health Canada announced that chlorinated paraffins with chain lengths greater than C18 are not harmful to human health.

In October 2011, Environment Canada placed chlorinated paraffins with chain lengths between C10 and C20 (this covers the SCCP, MCCP classes and part of the LCCP class) on the CEPA Toxic List. A notable factor is that Environment Canada decided to include three chain lengths in the LCCP class (C18-C20) on the CEPA Toxic List. Future work will involve resolving this issue with the chlorinated paraffin industry.

EPA fined Dover Chemical $1.4 million in February 2012 for violating TSCA. Dover Chemical will submit PMNs for MCCPs and LCCPs as part of the settlement with EPA. Further details can be found here.

In August 2012, EPA announced a similar settlement with INEOS Chlor Americas, which had been fined $175,000. The settlement is not final, as of the date of this article, because of the need for a 30-day public comment period. Additional information on this ruling can be found here.

Currently, EPA is in the process of conducting a further risk assessment review on MCCPs and LCCPs as part of a work plan announced in March 2012. Details are provided here.

EPA announced that these reviews would be completed in 2012, but provided no further details on when the results will be published. To date, EPA has not released details about its risk assessment reviews of MCCPs and LCCPs.

AQMD RULE 1144
There are basic points that a compounder/blender, distributor or end-user need to know about South Coast Air Quality Management District (AQMD) Rule 1144. Exact details can be found here. The highlights are:

• Rule 1144 regulates the VOC content of MWFs (cutting, grinding, drawing and stamping, heading, forming, quenching and rust protecting) and direct-contact lubricants (primarily slideway oils and lubricants for automatic screw machines) for end-users in the Los Angeles basin.
• As of July 1, 2012, the requirements are:

1. The five categories are regulated by VOC content as determined by ASTM E-1868-10. EPA Method 24 is not acceptable.
2. All containers sold into the AQMD area must have the VOC content on the label, no matter when made.
3. It is illegal to either use or sell fluids that exceed the limits. There are no exceptions unless an end-user applies for a formal variance from the AQMD.
4. Compounder/blenders must have records of how they determined the VOC of their products.
5. End-users are required to keep a purchase log of any products that exceed 50 gram/liter, but are within the maximum allowable VOC for the particular category.
6. Anyone who had direct sales to end-users was required to participate in the AQMD original survey, which was due by April 1, 2012. Additional surveys were due on the same date on April 1, 2013.

In August 2012, the AQMD reported that compliance among compounder/ blenders, distributors and end-users had been excellent, far better than the norm for new rules. However, AQMD, ILMA and STLE, among others, have been informing the regulated community about Rule 1144 for three years. If anyone is in violation of Rule 1144, they are “fair game” for fines and/or other sanctions, according to AQMD. The AQMD prefers to assist companies with compliance, rather, than punish them, so please contact them immediately.

The results of the sales survey were published Oct. 1, 2012. The report contained some aggregated data, but didn’t identify any particular company’s sales or products. Nevertheless, if there are any concerns, contact AQMD and request that all company-specific data be kept confidential.

Finally, AQMD released a paper about the science behind VOC as it relates to what they call volatiles, semi-volatiles and non-volatiles. They ran a six-month ambient condition evaporation study and compared those results to the various methods used for VOC determination. In particular, they found excellent correlation between ASTM E-1868-10 and their results for MWFs. The report also strongly refutes the concept of low- vapor pressure (LVP) solvents being non-VOC. While the California Air Resources Board allows the use of LVP solvents in consumer products, the report found that they completely evaporate, albeit a day or two later than more volatile solvents. This also matches what has been found with TGA testing. Copies are available from AQMD.

ASTM E1868-10
A key part of Rule 1144 is the new test method for determination of VOC in MWFs. In the past, formulators and end-users either used EPA Method 24 or reported no VOC from MWFs. EPA Method 24 was not designed for use on semi-volatile fluids such as MWFs. As a result of using EPA Method 24, the formulator or end-user will likely over-report VOC content of these types of fluids. In fact, EPA’s own Website instructs that “…Method 24 should only be applied to coating and printing type sources.” Taking an alternate view of this issue, it is possible to report no VOC from MWFs because there was no method available to test volatility for these fluids.

Rule 1144 uses a new method for determination of VOC in MWFs. This is ASTM E1868-10. A complete description of ASTM E1868-10 is available for a fee at www.astm.org. Method E1868-10 uses a time/temperature combination of 110 minutes at 81 C for determination of VOC. The method uses thermogravimetric analysis (TGA) to determine the weight loss over time. TGA is an extremely accurate method of ramping up and holding temperature and determining weight loss. A basic lab oven, such as suggested by EPA 24, cannot hold temperatures as close as TGA. Initial testing of EPA 24 by AQMD indicated that semi-volatile fluids displayed very poor repeatability and, thus was not a reliable test method for VOC determination.

Since the ASTM method is a weight loss over time, any volatile material will be defined as VOC. Water is present in many MWFs, so determination of water content and deleting that value from the calculations is required. Water content can be determined by knowing how much water is in the actual formula, as in the case of dealing with the neat product. Another method is using Karl Fischer (KF) titration for determination of water content and then delete that value from the calculations.

Method 1868-10 further specifies the weighing pan dimensions, pan metallurgy and fluid volume to be tested. This is a very sensitive method where even a slight variation of any of the test parameters will skew the final VOC value.

In comparison to EPA 24, the end-user will get more consistent results and, in some cases, lower values using ASTM E1868-10.

REFERENCES
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