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For those
with a scientific/technical background, the following information will be of interest. |
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| Petroleum
base oils |
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Past formulations of mineral base oils used in MRFs have been shown to
have the potential to cause dermatitis, oil acne, folliculitis and skin cancer. Some
studies have linked exposure to unrefined mineral oil lubricants to skin cancer. The
International Agency for Research on Cancer (IARC) has found sufficient evidence from
human epidemiology that mineral oils of various formulations that have been used in metal
machining operations can be carcinogenic to humans. Credible animal studies, often using
the mouse as a test subject, have confirmed the carcinogenic potential of many of the
early mineral oil lubricants. Analytical work performed over the years has identified
certain polycyclic aromatic compounds (PAC) as the causative agents. Historical
formulations of mineral oils used in metal removal operations were often derived from both
shale and petroleum oils and, prior to about 1950, many of these oils were essentially raw
distillates or only mildly refined. These early oil-based MRFs contained significant
amounts of PACs that resulted in cancer hazards to those exposed to them. Work practices
in the 1920s and 1930s were significantly different from those prevailing today and often
resulted in heavy dermal, inhalation and ingestion exposures. In 1984, the International
Agency for Research on Cancer (IARC) reviewed petroleum lubricant base oils and products
derived from them. IARC noted in their review the following:
The processes used to produce lubricant base oils and, correspondingly, product
formulations have changed considerably over the years. Until about 1940, processing
consisted of acid refining with clay finishing and subsequent dewaxing by chilling.
Solvent refining (and solvent dewaxing) was first introduced into the USA and in Europe in
the 1930s. Hydrotreating, as a newer, more severe process than "hydrofinishing"
was introduced in the 1960s. The trend has been to more highly refined oils with
associated removal of impurities including polynuclear aromatic compounds.
Since the late 1950s, most mineral oils used in the formulation of MRFs have undergone
severe solvent extraction and/or severe hydro treatment and, where properly used, these
treatments essentially eliminate the carcinogenic potential of the base oil. Modern severe
refining techniques of solvent extraction selectively remove PACs from base oils, and the
hydrogen treatment chemically disrupts the ring structures of PACs, producing non-ring
compounds.
The recycling of used industrial oils is becoming more popular as it avoids much of the
cost of purchasing new oils and almost all disposal costs. However, research has
demonstrated that some reprocessed oils may have unacceptably high levels of polycyclic
aromatic hydrocarbons (PAH). Unless the oil reprocessing involves severe refining
techniques, it is important that all reclaimed oil destined for reprocessing be tested;
any showing high levels of PAH should be segregated, and not processed for reuse as a
manufacturing lubricant.
It is now possible to routinely produce base oils for MRFs that have been shown,
through a variety of bioassays and screening tests, to be non-carcinogenic. However,
oil-based MRFs may be manufactured from a variety of sources, including reprocessed oils.
Therefore, it is recommended that organizations purchasing base oils for use in MRFs
request information from suppliers on the severity of treatment of those products prior to
their purchase and use. Analytical methods which measure the concentrations of polycyclic
aromatic compounds in base oils are the Institute of Petroleum IP 346 test, ASTM Method
E-1687-95, "Determining Carcinogenic Potential of Virgin Base Oils in Metalworking
Fluids," the Food and Drug Administration ultraviolet absorbency test and other tests
for total polycyclic aromatic content. The March 11, 1997 issue of Lubes n
Greases Magazine discusses a recent review of the scientific literature concerning
the potential for used MRFs to develop and accumulate levels of PACs that might represent
a hazard. Based on available data, the article concludes that there is little scientific
basis for health concerns from the generation of carcinogenic PACs in straight oils used
in metalworking.
In the USA, the advent of implementation of the Hazard Communication Standard in 1985
required chemical producers to label products and amend material safety data sheets (MSDS)
if they were determined to be carcinogenic or if they contained more than 0.1% of an
identified carcinogen. While oils that were not highly refined may have been used prior to
1985, manufacturers have discontinued such use. |
| Chlorinated
Paraffins (used as extreme pressure lubricants) |
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Straight oils, soluble oils, and semisynthetics may contain chlorinated
paraffins as extreme pressure (EP) lubricants. Extreme pressure additives are necessary
for many moderate to heavy machining operations. The chlorinated paraffins are typically
made by chlorination of various straight chain hydrocarbon C10-C50
feedstocks, most commonly paraffins or olefins. Chlorine content is from thirty to seventy
percent of the molecular weight of the additives. Some of the chlorinated paraffins have
shown cancer-causing capability in laboratory animals. The National Toxicology Program
(NTP) Seventh Annual Report on Carcinogens has listed chlorinated paraffins (C12,
60% Cl) as "reasonably anticipated to be carcinogenic to humans." For C23,
43% Cl, there was no evidence of carcinogenicity in male rats in high-dose two-year
studies, but there was equivocal evidence of carcinogenicity in female rats. Male mice,
however, showed significantly increased malignant lymphomas and were rated by the NTP as
showing clear evidence of carcinogenicity. These types of chlorinated paraffins are being
removed from many MRF formulations as acceptable replacement materials become available. |
| Reserve
Alkalinity |
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Reserve alkalinity is the presence of alkaline components in the fluid
that are available to react with acidic contaminants, such as carboxylic acids from
bacterial contamination. Reserve alkalinity helps to maintain the desired high pH of most
metal removal fluids. |
| Alkanolamines
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Virtually all synthetics and semisynthetics, as well as many soluble oils,
contain alkanolamines. These materials, which typically include both ethanolamines and
isopropanolamines, are present to provide reserve alkalinity and are the alkaline portion
of carboxylic acid and boric acid salts included to provide corrosion protection. Each of
the three ethanolaminesmonoethanolamine (MEA), Diethanolamine (DEA), and
triethanolamine (TEA)are or have been used in metal removal fluid formulations,
depending on the application and other requirements. EPA requires that labels for metal
removal fluids containing amines carry a warning against adding nitrites to such fluids.
In May, 1993, the U.S. Environmental Protection Agency issued a Significant New Use Rule
for alkali metal nitrites intended for use in metal removal fluids. |
Diethanolamine |
Diethanolamine has been a common alkanolamine in many metal removal fluid formulations.
It is produced as a primary chemical and it is a contaminant in commercial grade
triethanolamine. Concern over liver and kidney target organ effects in animals has caused
use of diethanolamine in metal removal formulations to decline. Recently diethanolamine
has been associated by NTP with liver and kidney effects in laboratory animals. While this
chemical has not been listed as a human carcinogen, most suppliers of metal removal fluid
have eliminated it as a primary component of fluids and they are working to reduce its
concentration as a contaminant from triethanolamine materials.
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| Biocides |
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Most water-miscible metal removal fluids contain a chemical biocide that
kills a variety of microscopic organisms and provides protection from microbial
degradation. Biocides are formally referred to as "antimicrobial pesticides";
however, for the sake of familiarity, the more common term,"biocide," will be
used here. Uncontrolled microbial contamination can lead to rapid biodegradation of the
MRF. Signs of deterioration in MRFs include emulsion destabilization, the production of
noxious odors and "slime," and failure of the MRF to perform as designed.
Only biocides registered by the EPA for use in metalworking fluids should be used as
additives. The Federal Insecticide, Fungicide and Rodenticide Act (FIFRA) regulates the
use of industrial biocides, and requires that their manufacture, packaging, distribution
and use meet strict requirements. Biocides are officially known as "antimicrobial
pesticides." FIFRA requires extensive labeling of biocides. As a result, users often
assume that biocides present greater hazards than many other chemicals commonly used in
the metal removal process.Selection of the most effective biocide for a particular
operation is a key decision, and should depend on an analysis of the most important
considerations involved. For instance, is microbial contamination the source of a
particular problem and, if so, is a biocide the right way to control it? Knowledge about
the specific microbiological population and the effect of specific biocides on each
microbial species would be useful, but is usually not available. What is the cost
effectiveness of other means to control biological growth compared to the use of biocides?
And, finally, what are the risks presented to potentially exposed employees by various
biocide products?
A thorough understanding of the system to be treated is important in determining the
most effective product and the concentration that will achieve the desired results without
potentially having adverse consequences among exposed workers. Good microbiological
control is important, as biocides may destroy bacteria and fungi but not their associated
toxins. Typically, a MRF system will require both a bactericide and a fungicide to prevent
contamination problems, although some chemicals can act against both types of
microorganisms. It is important to select the correct biocide and appropriate
concentration for the problem at hand. The use of dipsticks can show operators which type
of contamination is prevalent. Dosing with the appropriate concentration is important,
because maintaining a system with low levels of biocide can promote the development of
microbial resistance to that biocide. Also, if a single biocide for both bacterial and
fungal control is used, too low a concentration may only knock back the faster growing
bacteria, leaving the fungi unaffected and free to continue growing. A common practice,
the mixing of multiple biocides in MRF systems, may complicate management of systems and
should be carefully considered.
Many biocides have as a key component chemicals known as formaldehyde-condensates,
which release formaldehyde in the bacterial cell in use. These products have received
close attention since formaldehyde was identified as a suspect carcinogen. Formaldehyde
and formaldehyde- condensates are in general quite toxic, but all biocides should be
considered potentially toxic to humans at high concentrations. A comprehensive recent
study of formaldehyde in the air in plants using triazine as a biocide in the MRF found
that employees working in a variety of metal removal operations were not exposed to
formaldehyde at or above the OSHA Action Level of 0.5 PPM or to concentrations that would
exceed the Short-Term Exposure Level of 2 PPM. The exception to this general finding was
for employees working for extended periods around poorly ventilated sumps.
Where employees are exposed to formaldehyde gas, its solutions, and materials that
release formaldehyde, OSHAs Formaldehyde Standard, Code of Federal Regulations Title
29, Part 1910.1048, applies. Employers are required to make Medical Surveillance
(1910.1048(l)) programs available for all employees exposed to formaldehyde at
concentrations at or above the Action Level of 0.5 PPM, or the Short-Term Exposure Level
of 2 PPM (1910.1048(l).
Many biocides are human sensitizers and, depending on individual variation and
conditions of exposure, may have the potential to cause problems even if concentrations
are not excessive. It should be noted that toxicological dose responses are typically not
linear. A thorough understanding of the particular conditions a biocide is intended to
correct is important in determining the most effective product and concentration that will
do the intended job and not have potentially adverse consequences among exposed workers.
This is especially important as some biocides may destroy bacteria and fungi, but not
their associated endotoxins. Since bacteria are in general more susceptible to some
biocides than fungi and yeasts, it is important to be sure that both the correct biocide
and appropriate concentrations are used. Too low a concentration of biocide may result in
differential growth of fungi. A common practice, the mixing of multiple biocides in MRF
systems, may complicate management of systems and should be avoided.
Under no circumstances should chlorine bleach be used as a biocidal
additive in a MRF system. |
| Mist
suppressants |
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Mist suppressants can be an adjunct to, and possibly an alternative to,
enclosure and ventilation for the control of metal removal fluid (MRF) mists. Not only can
they effectively reduce mist levels in many applications, but they can do so more quickly
and with lower engineering costs, capital expenditures, and operation costs, all with a
minimum interruption of production. Mist suppressants are dissolved polymers that work
by increasing the elongational viscosity or elasticity of the fluid, increasing the size
of the mist droplets and thereby reducing the amount of suspended mist. Examples of
suppressants are polyisobutylene (PIB), used with straight oil, and polyethylene oxide
(PEO), polyacrylamide, and sulfonate polymers used in soluble oils and synthetics. The
amount of polymer needed varies with the MRF and the polymer type, generally in the range
of 100 to 1000 PPM. Mist reductions of approximately 50 percent are generally expected,
with as much as a 90 percent reduction with PIB in certain applications.
Commercially available polymers used for mist suppression are broken down by shear
force in the machining and pumping processes. Polymer levels must be monitored and
adjusted. In some cases, a constant addition is required. The additives should not
adversely effect the machining operation. No adverse effects on tool wear, part finish,
filter life, etc., are acceptable. It should be noted that PEO has some potential for
increased Chemical Oxygen Demand (COD), which may
affect water treatment. These mist suppression polymers may also affect filter life.
The generation of oil mist levels in association with high-speed machine tool
operations where straight oils are used as a major component of the MRF can be a serious
health and fire safety problem. Straight oils atomize readily and produce aerosols that
remain in the ambient air for long periods. Straight oils are often necessary to achieve a
high-quality surface finish, and thus are an important component of modern quality
machining operations. One promising approach to reducing the amount of oil mist generated
by machining operations involves the use of high molecular weight polymers that are
dissolved in the MRF in very low concentrations.
It should be noted that this technique has not worked equally well in all
systems. Experimental work performed on dilute solutions of polyisobutylene in mineral oil
demonstrated that, when atomized, they produced droplets that were on average much larger
than oil without the polymer. With a larger average size of droplet, there are fewer drops
generated, and their settling rate is greatly increased. In one study, where 20 parts per
million of polyisobutylene were added to oil-based MRFs, oil mist concentrations were
reduced by 80-90% with no adverse effects on the quality of the machining. This mist
suppression can be achieved at a cost of $10 to $100 per week for a 10,000-gallon system.
Work is progressing on a similar system for water-based MRF.
A useful discussion of this topic can be found in "Polymer Additives as
Mist Suppressants in Metalworking Fluids: Laboratory and Plant Studies," by Esin
Gulari, Charles W. Manke, Joseph Smolinski, Richard S. Marano, and Louis Toth in The
Industrial Metalworking Environment: Assessment and Control, Symposium
Proceedings, November 13-16, 1995, pp. 294-300. |
| Toxicity |
Useful toxicity references include ASTM Guide E 1302,
which describes procedures to assess the acute toxicity of water-miscible metal removal
fluids, and ASTM Method E 1687, which describes a test method to screen for the
presence of potential skin carcinogens in metal removal fluids.
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| Volatile
Organic Compounds (VOC) |
Metal removal fluids contain a variety of organic
components of varying vapor pressure. Some of the more volatile compounds may be
considered volatile organic compounds
(VOC) in your state. Selecting fluids without highly volatile components may reduce
regulatory permitting or reporting requirements. Most water-diluted metal removal fluids
will not contain obvious VOC materials. However, when tested using methods developed for
water-based coatings such as ASTM Method 2369 (Standard Test Method for Volatile Content
of Coatings) or Method 24 of 40 CFR part 60, Appendix A, they often give non-zero results.
Many plants, especially the auto industry, must use these results to calculate their VOC
emissions under the Clean Air Act. Consult the manufacturer for information regarding VOC
in light of local, state, and federal air emissions regulations.
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