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United States Office of Water EPA-821-R-93-015
Environmental Protection (WH-552) September 1993
Agency
oEPA Oil and Grease Workshop
Boston, Massachusetts
June 30,1993
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DISCLAIMER
This report has been reviewed by the Analytical Methods Staff of the EPA Office of Water. It is in-
tended to inform the public about EPA's efforts to replace Freon-113 in Agency analytical methods.
Mention of company names, trade names or commercial products does not constitute endorsement or
recommendation for use.
Questions or comments regarding this report should be addressed to:
William A. Telliard, Chief
Analytical Methods Staff
Engineering and Analysis Division (WH-552)
Office of Science and Technology
Office of Water
401 M Street, S.W.
Washington, D.C. 20460
ACKNOWLEDGEMENTS
This report was prepared under the direction of William A. Telliard with assistance from the Environ-
mental Services Division of DynCorp Viar, Inc. (under EPA contract no. 68-C9-0019).
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MEETING SUMMARY
OIL AND GREASE WORKSHOP
BOSTON, MASSACHUSETTS
JUNE 30, 1993
ANALYTICAL METHODS STAFF
ENGINEERING AND ANALYSIS DIVISION
OFFICE OF SCIENCE AND TECHNOLOGY
OFFICE OF WATER
U.C. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
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Introduction
The Analytical Methods Staff of the Office of Science and Technology's Engineering and
Analysis Division (within the U.S. EPA Office of Water), held a public workshop on the subject
of the Agency's Oil and Grease Freon Replacement Study at the EPA Region I Conference
Center in Boston, Massachusetts on June 30, 1993.
The Oil and Grease Workshop was intended to inform the public about EPA's efforts to
find a replacement for Freon 113 in its analytical methods for oil and grease, and to provide a
forum for public comment. The date, time, place and purpose of the workshop were advertised
in the Federal Register on June 8, 1993.
The Oil and Grease Freon Replacement Study, is more fully described in a report entitled
Preliminary Report of EPA Efforts to Replace Freon for the Determination of Oil and Grease,
EPA-821-R-93-009, June 1993. Briefly, EPA is seeking a replacement solvent for Freon 113
in three Agency methods for "total recoverable oil and grease" because production and sale of
Freon 113 and other Class I ozone depleting substances will be banned by January 1, 1996 under
both the Clean Air Act Amendments of 1990 and the Montreal Protocol on Substances that
Deplete the Ozone Layer. The Freon Replacement Study is a cooperative effort among the EPA
Offices of Water, Solid Waste, and Air and Radiation, with the voluntary participation of a
number of instrument manufacturers and vendors. The first phase of the study involved
exploration of the use of five alternative solvents and two alternative techniques that were tested
on a suite of actual industrial and commercial aqueous and solid waste samples. The results of
EPA's statistical analysis of the Phase I study data for conventional and alternative techniques
were presented at the workshop.
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Meeting Summary
This document summarizes the information presented at the workshop by EPA and
invited speakers, as well as questions and comments from the audience. The workshop agenda
is attached as Appendix A. The visual aids used by the speakers are provided in Appendices
B through H.
Welcome: Kevin McSweeney, U.S. EPA Region I
Mr. McSweeney welcomed the participants to Boston and introduced Mr. Telliard as the
workshop chairman.
Freon Replacement Method Study:
Technology
William A. Tellianl, U.S. EPA Office of Science and
The first speaker was William A. Telliard, Chief of the Analytical Methods Staff within
the Office of Water's Engineering and Analysis Division. Mr. Telliard is responsible for
direction of the Oil and Grease Freon Replacement Study.
Mr. Telliard reviewed the regulatory history of chlorofluorocarbons, including the 1990
Clean Air Act Amendments (CAAA) and the Montreal Protocol on Substances that Deplete the
Ozone Layer. He noted that Freon 113, the solvent used in the oil and grease measurement, is
regulated by the CAAA and the Montreal Protocol and will be phased out of use by 1996. He
stated that oil and grease is an old method which was first used in sanitary chemistry to study
the effects of ail Imhcf tank on removing large particulates from sewage to prevent sewer
plugging. Mr. Telliard pointed out that oil and grease is a "method-defined" parameter whose
result depends on the solvent that is used. Historically, carbon tetrachloride was used, then n-
hexane, and most recently Freon 113.
He then described Phase I of the Freon Replacement Study. The purpose of the first
phase of this study was to continue the Agency's investigation of replacement solvents to identify
a solvent that yields results equivalent to Freon 113, or failing that, to select a solvent(s) or
alternative technique(s) for further study. The five alternative solvents evaluated in Phase I were
n-hexane, an 80:20 mixture of /i-hexane/methyl tertiary-butyl ether, metnylene chloride,
perchloroethylene, and DuPont 123 (2,2-dichloro-l,l,l-trifluoroethane.)
Mr. Telliard indicated the scope of the problem that EPA faces in changing the oil and
grease method by pointing out that oil and grease is a regulated parameter in approximately
10,500 National Pollutant Discharge Elimination System (NPDES) permits and in effluent
guidelines for 25 industries. He stated that in order to obtain realistic results, Phase I of the
study tested "real world" samples from 39 plants in 24 industrial categories, including
approximately 41 aqueous wastes and 30 solid wastes. These samples represented oil and grease
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of animal, vegetable and mineral (petroleum) origin. He noted that both solid phase extraction
(SPE) and infrared techniques were evaluated in the first phase of the study. He stated that all
of the industrial plants that had been visited and sampled were effectively removing oil and
grease from their effluents with the treatment equipment they had installed. Many plants had
to be sampled upstream from the final effluent to detect significant amounts of oil and grease.
Mr. Telliard's presentation materials may be found in Appendix B.
Mr. Telliard then introduced Roger Litow, who was to speak on the statistical analysis
of the Phase I study data.
Statistical Analysis of Phase I Study Data: Roger Litow, DynCorp Viar, Inc.
Mr. Litow discussed the results of the statistical analysis of the study data. He began by
discussing the statistical measures of similarity between solvents that were used in the study and
described in the June 1993 report distributed to the workshop participants. He explained that
the "solvent- to-Freon ratio" used in the report is not the primary measure of similarity because
it does not account for variability in the data and tends to cancel out the effects of samples
whose alternative solvent results were higher than Freon for some samples and lower for others.
Mr. Litow explained that the solvent-to-Freon ratio was used in an attempt to find "correction
factors" to convert alternative solvent results to be equivalent to Freon.
He then described the data transformation that was needed to make the study data
amenable to analysis of variance (ANOVA). He noted that the variability of the results increases
with increasing concentration, rather than being constant (this violates the assumptions of
ANOVA). To compensate for this problem, he stated that the data had been log-transformed
to eliminate this "heteroscedasticity". A constant was added to bring negative results above zero
so that logarithms could be taken. The constant also reduced the influence of the lower results
on the ANOVA.
Mr. Litow then described the Root Mean Square Deviation (RMSD), which was used as
the primary measure of statistical similarity between Freon 113 results and alternative solvent
or technique results. He noted that this measure accounts for variance both above and below
the results obtained with Freon 113.
He then recounted the stratification of the study data to find groupings for which
equivalent results for Freon 113 and other methods could be expected. Petroleum and non-
petroleum were the strata chosen. He presented three graphs (Exhibits 11-13 of the June 1993
report) showing RMSD results versus Acceptance Limits for aqueous samples by separatory
funnel extraction and for solid samples by Soxhlet and sonication extractions. He noted that n-
hexane and perchloroethylene were equivalent to Freon 113 in aqueous samples contaminated
with non-petroleum-based oil and grease. For Soxhlet extractions, n-hexane and the 80:20
mixture of n-hexane and methyl tertiary-butyl ether were equivalent to Freon 113 for petroleum-
contaminated samples. For the sonication extraction, only perchloroethylene in non-petroleum
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samples was equivalent to Freon 113 (Soxhlet results).
He then presented two graphs (Exhibits 14 and IS of the June 1993 report) showing the
RMSD results for each of the alternative techniques evaluated in the study. For non-petroleum
samples, he noted that the (Varian) SPE column using /i-hexane or 80:20 was equivalent to
Freon 113 (using separatory funnel). He cautioned, however, that that result was based only
on five samples and should be viewed with caution. Hie (3M) 90 mm SPE disk using Freon
113 gave equivalent results to Freon 113 with a separatory funnel. For petroleum-contaminated
samples, he noted that none of the alternative techniques were equivalent to Freon 113.
Mr. Litow concluded with a chart that summarized the solvents that yielded results
equivalent to Freon 113 for the separatory funnel, Soxhlet extraction and sonication techniques.
Perchloroethylene was equivalent to Freon 113 twice, /i-hexane twice, and 80:20 once. Mr.
Litow's presentation materials may be found in Appendix C.
Question and Answer Period
Question: A member of the audience asked if there were any theories to explain the
difference between water and solid matrices, relative to influencing the TSS (total
suspended solids)?
Answer: Mr. Telliard replied that there was as yet no satisfactory explanation.
Mr. Telliard then briefly described some experimental work with solid phase extraction
(SPE) cartridges done in the EPA Region III Central Regional Laboratory. He introduced the
next speaker, Mr. Rex Hawley, who had cooperated with and furthered those studies.
Evaluation of Solid Phase Extraction Columns for Analysis of Oil and Grease in Aqueous
Samples: Rex Hawley, Varian Sample Preparation Products
The first speaker on SPE was Rex Hawley of Varian Sample Preparation Products. He
described work done with SPE cartridges that were improved on the basis of problems
encountered during Region Ill's work. Mr. Hawley stressed simplicity, error reduction, low
cost, and rapidity, as well as reduced solvent usage as advantages of using SPE. Mr. Hawley
presented the apparatus used in Varian's work, including both common laboratory apparatus and
specialized components. He outlined the basic procedure used to prepare the equipment and
analyze a sample. He discussed an evaluation of filter materials and a technique to remove water
from the eluent without using sodium sulfate (an Aquasep filter.) He presented the results of
tests run with Varian's SPE cartridges on synthetic standard samples (Mazzola oil in deionized
water) versus the results obtained by the EPA separatory funnel method, and indicated that good
agreement was obtained. Comparable results were also obtained for samples collected by the
Los Angeles County Water District. Mr. Hawley then discussed the results of analyses of
samples provided by EPA. Some of these samples were difficult to analyze because of high
solids contents, which caused long elution times. This problem was circumvented by the use
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of several SPE columns per sample. Finally, Mr. Hawley discussed the distinction between
extraction solvents in liquid/liquid extraction and elution solvents in SPE. Mr. Hawley's
presentation materials may be found in Appendix D.
Question and Answer Period
Mr. Telliard commented that SPE offers the advantage of being able to extract a sample
in the field, and then ship it to a laboratory for elution and analysis.
Question: A member of the audience asked if the difference in recoveries among the various
elution solvents could be due to differences in the materials extracted by the
solvents (using SPE).
Answer: Mr. Hawley replied that within the SPE results, there were no great differences
among the results for various solvents. He also stressed that the results would be
different for a particular solvent used with liquid-liquid extraction versus SPE,
because the principles of the two techniques are different. In SPE, the solid
phase media does the extraction, and the solvents merely elutes extracted material
off the SPE cartridge. Mr. Telliard reinforced this point by stating that the
variability in the SPE method comes from the solubility of the extracted material
in the elution solvent, rather than from the extraction by the SPE medium.
Question: A member of the audience asked if the final determination was done
gravimetrically.
Answer: Mr. Hawley answered that it was.
Question: A member of the audience asked if the boiling point of the elution solvent made
any difference in the results.
Answer: Mr. Hawley answered that the elutropic properties of the solvent, not the boiling
point, are what matter.
Question: A member of the audience asked if the fact that the boiling points of some of the
materials measured are lower than those of the solvents tested makes any
difference to the results.
Answer: Mr. Hawley said that it did not, because oil and grease is defined in the method
as materials boiling over 70 °C.
Mr. Telliard commented that the two samples that were the topic of the preceding
questions, one from a leather tannery and one from a railroad yard timber treating area, were
challenging samples for which inconsistent results might be expected.
Question: A member of the audience asked about the capacity of the SPE column (in terms
of weight retained).
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Answer: Mr. Hawley replied that the capacity of the columns tested, which have a five-
gram bed of SPE material, could be as high as 1,000 mg, and that since the
sample bottle is still connected to the system when the elution is done, that oil
and grease retained on the walls of the bottle would also be eluted.
Question: A member of the audience asked how the volume of solvent used to elute the SPE
column was chosen, given the question of the column capacity.
Answer: Mr. Hawley answered that he had conducted experiments that showed that one
20 mL aliquot and one 10 mL aliquot of elution solvent were sufficient to elute
all but one or two mg of oil and grease.
Question: A member of the audience asked a question about having a second cartridge in
the SPE experimental apparatus.
Answer: Mr. Hawley explained that for samples with large amounts of particulates, the
SPE cartridge may become clogged. When this happens, the sample bottle may
be separated from the apparatus, righted, a new cartridge attached, and the
extraction restarted.
Question: Mr. Telliard asked if both SPE cartridges were then eluted.
Answer: Mr. Hawley replied that they both were eluted.
Mr. Telliard commented that the ability to use multiple cartridges offered flexibility when
extracting samples with high oil and grease contents.
Question: A member of the audience asked for more information on the use of the AquaSep
column in the experimental apparatus to remove water.
Answer: Mr. Hawley described the position of the AquaSep column as being below the
SPE column, which allows the eluting solvent, but not water, to drip through to
the collection box.
Oil and Grease Analysis in Wastewater Using Solid Phase Extraction Disks: Craig Markell,
The 3M Corporation
The third speaker on SPE was Craig Markell of the 3M Corporation, who discussed work
done with their 47mm and 90mm SPE disks. He began by reviewing the principles of solid
phase extraction in comparison to liquid/liquid extraction. Next he showed some photographs
of the SPE disks, including a micrograph of the spherical SPE material. He described the
efficiency of the SPE disks by showing a picture of a disk which had been used to extract an
orange dye from water. He then showed some pictures of a six-place manifold with a process
controller used for multiple extractions.
Mr. Markell presented some information on types of compounds that may be extracted
with SPE, noting that substances with water solubilities up to about 1/10 of 1% could be
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extracted. He noted that higher results will be obtained in the oil and grease test when
compounds that may be neutral or ionic (such as phenol) are in their protonated (neutral) form,
as at pH 2. He also noted that high salt concentrations (ionic strength) in the sample will change
the partition coefficient and result in greater extraction. Mr. Markell then discussed the capacity
of SPE devices, stating that capacity is greater for hydrophobic compounds and smaller for
water-soluble compounds.
He then outlined the method used with the SPE disks including sample sizes, elution
times and solvent aliquot volumes, and the drying step using sodium sulfate. Sodium sulfate was
eliminated from the sample using a syringe-end filter. He presented a diagram of an SPE disk
in its holder with the filter aid material on top. He explained that a filter aid such as glass beads
was useful to avoid overloading the SPE disk, especially if the sample contained free-phase oil.
He presented results for five solvents on a number of different samples, showing that generally
higher results were obtained with more polar solvents (he contrasted this result with what Mr.
Hawley had said earlier about the elution solvent not making a difference in the results). Mr.
Markell then presented results of the analysis of some of the Phase I study samples, showing
general correlations for two groups of high and low concentration samples. He presented
precision data for the SPE disk method, which ranged from 0 to 23% difference. He concluded
by saying that, whUe nothing will duplicate Method 413.1 (the EPA oil and grease method using
Freon 113 and a separatory funnel) exactly, SPE disks do work for oil and grease. Mr.
Markell's presentation materials may be found in Appendix E.
Question and Answer Period
Question: A member of the audience asked if Mr. Markell had any data on the effect of
sample salinity on SPE extraction.
Answer: Mr. Markell replied that he did not have any such data for the oil and grease
method, but work he had done on more polar analytes such as phenol confirms
the "salting out" effect for neutral compounds and also shows the expected lower
recoveries for ionic compounds due to higher ionic strength.
Question: The same questioner asked for clarification of Mr. Markell's answer in terms of
the function of the CIS packing.
Answer: Mr. Markell answered that salt changes the partition coefficient of water in
contact with the bonded phase (C18 packing.)
Question: The same questioner expressed doubt that the partition coefficient was as
important in SPE as in liquid-liquid extraction.
Answer: Mr. Markell suggested that they talk about this issue in more detail later.
Mr. Telliard noted that the questioner was referring to "produced water" which has a
high salt content, and that high salt content did not interfere with extraction of organic
compounds, as was shown in the study report.
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Mr. Telliard then introduced the next speaker, William Eckel of DynCorp Viar.
Evaluation of Oil and Grease Samples using NDIR and Flon S-316:
DynCorp Viar, Inc.
William Eckel,
Mr. Eckel described the use of the Horiba OCMA 220 nondispersive infrared (NDIR)
analyzer for determination of oil and grease using a modification of EPA Method 413.2. A
proprietary solvent, Flon S-316, that was originally used in a continuous on-line process monitor
where a high boiling point was required, is used in the OCMA 220. Horiba used this instrument
to analyze 38 samples collected during Phase I of the study. Mr. Eckel stated that the Horiba
instrument extracts 15 mL of sample with IS mL of solvent, and measures the absorbance at
2930 reciprocal centimeters without evaporating the solvent. He said that this should lead to
higher results than are obtained with Method 413.1, because the lower-boiling oils are not boiled
away with the solvent. Mr. Eckel described the Horiba instrument as a non-dispersive infrared
analyzer, meaning it does not scan wavelengths. He stated that, of all the solvents tested in the
study, only perchloroethylene could also be used in the Horiba instrument, since that solvent
contains no hydrogen and therefore has no carbon-hydrogen stretch in its IR spectrum.
(Perchloroethylene was not tested in Phase I by Horiba, however.)
He then showed results of analyses for Phase I study samples. He began with Exhibit
10 from the June 1993 report, which indicated that the Horiba results were 60% higher than
Freon 113 overall, 20% higher for petroleum-based samples, and over twice as high for non-
petroleum samples. He noted that the RMSD results showed that the Horiba results were not
equivalent to Freon 113 and then described difficulties with the extraction of some of the more
challenging samples. Emulsion-free extractions were obtained by shaking samples with solvent
in 40 mL VOA vials.
Results for 38 samples showed that 17 results were higher than the Freon 113 separatory
funnel method, 17 were lower, and four were below 5 mg/L by both methods. Mr. Eckel then
displayed Exhibits 14 and 15 of the June 1993 report to show how the Horiba analyzer compared
to the other alternative techniques for non-petroleum samples and petroleum samples,
respectively. Finally, he showed Exhibit 16 which showed the mean solvent-to-Freon ratios for
all of the alternative techniques including Horiba.
Mr. Eckel concluded that, because of their increased sensitivity and reduced solvent
usage, infrared techniques would continue to be considered for the determination of oil and
grease. Mr. Eckel's presentation materials may be found in Appendix F.
Question and Answer Period.
Question: A member of the audience asked if the performance of Freon 113 in the Horiba
analyzer had been tested and compared to Flon.
Answer: Mr Eckel replied that Horiba had not used Freon 113 to analyze any of the Phase
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I study samples. He further noted that all alternative techniques in the study were
compared to the results obtained with Freon 113 and EPA Method 413.1
(separatory funnel or Soxhlet extraction and gravimetric determination).
Mr. Telliard commented that Horiba also offers a solvent reclamation system to recover
the Flon solvent.
Question: A member of the audience asked if there was any problem obtaining a
representative 15 mL sample from a liter of water that is inherently a two-phase
system of oil and water.
Answer: Mr. Telliard answered that while he believed analysis of the entire one-liter
sample would be more representative, he had no data to prove it. He indicated
that the issue of sample representativeness (including the issue of grab samples)
would be addressed in Phase II of the study.
Question: A member of the audience asked if the Horiba instrument had been tested with
prepared standards, rather than just collected samples.
Answer: Mr. Telliard replied that the manufacturer had analyzed standard samples. He
also noted that the SPE and infrared techniques discussed were for aqueous
samples only.
Mr. Telliard then introduced the next speaker, Gerald DeMenna of Chem-Chek
Consulting/Buck Scientific.
Determination of Oil and Grease by Evaporation of Solvent in a Quartz Cell in an Infra-red
Spectrophotometer: Gerald DeMenna, Chem-Chek Consulting/ Buck Scientific
Mr. DeMenna began by describing the difficulties his laboratory has had in obtaining
good results with the oil and grease test using a variety of techniques and solvents. He then
described a procedure developed in his laboratory that is designed to yield results similar to the
EPA gravimetric method now in use. The new method uses the same sampling and extraction
methodology as before, but uses infrared spectroscopy to make the final determination. A new
quartz evaporation plate/infrared cell was developed specifically for this use. In the proposed
procedure, smaller amounts of sample (100 mL versus one liter) and solvent are used in the
extraction. Mr. DeMenna asserted that good correlation with tests run with a full liter of sample
is obtained when using only 100 mL of sample. A thin film of oil and grease is cast by
evaporation of an aliquot of the extract in the quartz plate and this is placed in the open sample
compartment of an infrared analyzer.
Comparative analyses were performed between the quartz plate evaporation technique,
a normal liquid quartz cell technique (similar to EPA Method 413.2) and Method 413.1. For
the liquid cell technique, extractions are carried out in screw-cap cells used for GC headspace
analysis to avoid evaporation. These filled cells are placed in the beam of the IR analyzer and
the hydrocarbon materials are measured as absorbance, transmission units or directly in parts
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per million. For the new evaporation technique, the final gravimetric determination of Method
413.1 has been replaced by measurement in a high signal-to-noise infrared photometer. These
three techniques were compared using a standard mixture of isooctane, hexadecane and
chlorobenzene.
The evaporation plate technique has the advantage of using far less solvent. Mr.
DeMenna discussed the construction of the quartz IR evaporation plate and the method of
pipetting the sample into it. A 250 uL portion of the extract is pipetted into a quartz plate with
a 300 uL cavity. The solvent is evaporated away at 75+1-2 °C on the heat fins of the infrared
analyzer, and the absorbance of oil and grease measured at 3.4 microns (2950 wave numbers).
Infrared analyzers with closed cells or flow cells are not amenable to the new technique.
Mr. DeMenna presented some results from environmental samples taken in northeastern
states, comparing the EPA gravimetric method (413.1), his new quartz plate/evaporation method
and the quartz liquid cell technique (413.2.) All techniques were performed with Freon 113.
His results showed that his new quartz evaporation plate method gave slightly higher results than
the EPA gravimetric method, and slightly lower than the quartz liquid cell method. Precision
was comparable for the three methods, and spike recoveries were good.
He described an experiment performed after a similar workshop was held in Norfolk, Va.
on May 4, 1993. The purpose of this experiment was to compare Freon 113 and methylene
chloride. Results with methylene chloride on a brackish water sample were 30 to 50% higher
than with Freon 113.
Mr. DeMenna then discussed the detection limit and linear range of the IR quartz
evaporation plate technique. The detection limit at 0.004 absorbance units was 1.5 ppm, and
response was linear to 250 ppm.
He concluded by saying that the new technique offers higher throughput in the laboratory,
reduced solvent usage, and is adaptable to any IR instrument with an open sample compartment.
Mr, DeMenna's presentation materials may be found in Appendix G.
Question and Answer Period
Question: A member of the audience asked if Mr. DeMenna had any problems with the oil
and grease residue running out of the cavity in the quartz plate after evaporating
the solvent.
Answer: Mr. DeMenna answered that residues of up to 500 ppm isooctane, hexadecane
and chlorobenzene did not present any such problems.
Question: A member of the audience asked if there had been any problems with bumping
when boiling off the solvent.
Answer: Mr. DeMenna answered that no boiling was involved in the work he had done.
The solvent was evaporated away by placing the quartz plate on the heat fins of
the IR instrument. He also mentioned some experiments he had done that showed
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that no residual solvent was left after 60 seconds of evaporation.
Strategy Options for Regulating Oil and Grease: William A. Telliard, U.S. EPA Office of
Science and Technology
Mr, Telliard then discussed the policy options being considered at EPA to resolve the
problem of Freon 113 use in the oil and grease method. He noted that the Canadian government
was also studying this problem, and that they, as well as he, were leaning toward n-hexane as
the replacement solvent. He explained that n-hexane was originally an alternative solvent to
Freon 113 in the standard method, but was later dropped. He stated that generally lower results
are obtained with n-hexane than with Freon 113, so that switching to n-hexane should not cause
(NPDES) permit holders to become noncompliant.
Mr. Telliard recalled that the issue of /i-hexane's neurotoxicity had been raised at the
Norfolk workshop, so that he intended to investigate the applicability of cyclohexane to both
gravimetric and solid phase extraction techniques in Phase II of the study.
He then discussed the other alternative solvents. He stated that perchloroethylene would
be retained in the study, because results equivalent to Freon 113 were obtained for some solid
samples with sonication and because it could be used with infrared techniques. Turning to the
80:20 mixture of n-hexane and methyl tertiary-butyl ether, he stated that, contrary to what his
slide said, he had decided to drop further consideration of that solvent. He cited laboratory
safety and solvent storage (evaporation resulting in a ratio other than 80:20) considerations as
his reasons. Methylene chloride would be dropped, he said, since it had produced no results
equivalent to Freon 113. He also said that DuPont 123 would be dropped since it is a Class II
chlorofluorocarbon scheduled for phase-out, and because it had positive results in some
mutagenicity tests.
Mr. Telliard stated that he wanted to continue to investigate solid phase extraction and
infrared techniques.
He then turned to a discussion of policy options. The first option he presented was to
do away with the oil and grease method. This was suggested often by commenters. He noted
that while this was still a viable option, it would not be easy to implement.
He also mentioned the possibly of modifying the method by adding cleanup procedures
that would provide more definitive separation of polar and nonpolar materials. He stated that
this option would be considered in Phase II.
The third option he presented was to obtain a waiver under the Clean Air Act
Amendments of 1990 to allow continued use of Freon 113 for this purpose. He noted, however,
that with the approaching ban on Freon 113, and its high cost, this was not a viable option.
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The fourth option he presented was to develop a correction factor to correct results for
an alternative solvent to what would have been obtained using Freon 113. He stated that this
could take the form of demonstrating the performance of a given solvent, and then reverting to
that solvent at the time of permit renewal. He mentioned that this approach would be in line
with the current concept of "performance-based" methods.
The fifth option was for EPA to select one solvent or extraction technique that produces
results closest to Freon 113. At this point, the likely choice would be n-hexane or cyclohexane
with some cleanup steps.
The sixth option was to select more than one solvent, since some solvents work better
with petroleum-based materials and others with non-petroleum-based materials. Mr. Telliard
noted that additional data would be needed to support such a decision, and that there was not
sufficient time to collect it before a decision needed to be made.
The seventh option presented was to give further consideration to alternative techniques,
such as gas chromatography (GC) and infrared. He noted that the Office of Water had used the
petroleum hydrocarbons method (using GC) for the Offshore Oil and Gas Industry and
Petroleum Refining Industry studies, and that IR was a widely used screening tool. He raised
the issues of comparability between methods and the higher cost of these other measurements
as issues to be overcome. He stated that this might be the most technically sound option, but
that it would be difficult to revise the many regulations and permits that are based on gravimetric
data. He said mat more than one technique could be chosen, in line with the Agency's
performance-based methods approach.
Mr. Telliard again noted that the Canadians were leaning toward n-hexane. He said EPA
was focusing on n-hexane or cyclohexane, and solid phase extraction. He stated that if there
were truly no significant change in regulatory monitoring results (NPDES testing for oil and
grease) by going to the alternative solvent, that a correction factor would not be needed. He
qualified this by saying that EPA would have to state that a switch to the leading solvent would
mean less strict regulation than with Freon 113. Mr. Telliard's presentation materials may be
found in Appendix H.
Mr. Telliard then opened the floor for questions and discussion.
Question and Answer Period
Question: Mr. Hawley asked if pentane was being considered, as suggested at the Norfolk
Workshop.
Answer: Mr. Telliard answered that it was not, due to laboratory safety issues (as with
petroleum ether, of which pentane is the predominant component.) Mr. Litow
added that its boiling point was also an issue, since it boils at room temperature
at high altitudes.
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Question: A member of the audience asked if supercritical fluid extraction (SFE) was being
examined for solid samples.
Answer: Mr. Telliard replied that an Office of Solid Waste workgroup was studying SFE,
and that a subgroup of the workgroup was looking at SFE for elution in solid
phase extraction (SPE.) He noted that all of the solvents have their drawbacks,
and that SFE would be a nice way to go if it were commercially available.
Question: A member of the audience recounted his experience of switching away from
gravimetric to an infrared method, and asked why a new solvent rather than an
alternative method such as IR was being contemplated.
Answer: Mr. Telliard answered that his immediate mandate was to solve the issue of the
gravimetric method, and to do it by December.
Question: A member of the audience commented that compliance monitoring will be
problematic when there is a local limit across many industrial categories, and a
new solvent measures different substances than before, depending on what is in
the wasiewater. Another comment related to the previous question, and asserted
that infrared methods would give results more than 10% higher than gravimetric
methods. Finally, it was asserted that substances that are not oil nor grease cause
positive oil and grease results using the present methods.
Answer: Mr. Telliard answered that the method name "oil and grease" is a misnomer,
since what the method actually measures is what comes out of the solvent. He
commented that the oil industry is concerned that the method measures sulfur and
other non-oil substances. He repeated that the ultimate answer may be to replace
the oil and grease method, but that the issue at hand was to replace Freon 113.
Question: A member of the audience asked if performance-based methods would be the best
way to establish an infrared method.
Answer: Mr. Telliard replied that it would be, but cautioned that the comparability of the
methods was not established, and it would expensive to do so.
Question: A member of the audience asked if laboratories would continue to be urged to
reclaim their solvent after the solvent change had been made.
Answer: Mr. Telliard replied that they would.
Question: The same questioner stated that solvent recovery would be more difficult with
hexane.
Answer: Mr. Telliard agreed.
Question: A member of the audience asked what the timing and content of Phase II of the
study would be.
Answer: Mr. Telliard answered that it would start in a couple of weeks, and that it would
involve the solvents he had mentioned as being retained in the study as well as
solid phase extraction. He qualified this by saying that having a Phase II
13
-------
depended on obtaining funding, and that if time and money did not permit, then
the decision would be to go with hexane. He noted that because of the mandate
to do away with Freon 113, a proposed decision would have to go out for
comment by the end of the year, and would have to go final by early spring.
Question: A member of the audience asked how many rules (effluent guidelines) there were
for which oil and grease was limited.
Answer: Mr. Telliard replied that guidelines limit oil and grease discharges for 25
industries.
Question: The same questioner asked if not regulating oil and grease would cause
"backsliding" if other parameters also control the same pollutants.
Answer: Mr. Telliard answered that it probably would not, since many guidelines also
contain limitations on other conventional parameters such as BOD (biological
oxygen demand) and TSS (total suspended solids).
Question: A member of the audience asked if his industry could propose substituting an
alternative method, such as petroleum hydrocarbons by gas chromatography, if
the results could be shown to be reproducible and comparable to the Freon 113
method.
Answer: Mr. Telliard replied that this was possible, but that it would be difficult to prove
that the methods were "equivalent", since they are known to measure different
substances. He noted that the issue of an alternative measurement in lieu of oil
and grease was still on the table.
Question: The same questioner asked how to approach EPA with a question of method
equivalency.
Answer: Mr. Telliard replied that a "bridging package" involving the Assistant
Administrator for Water, the Office of Science and Technology, the Permits
Division and Enforcement Division and others would need to be put together to
advance such an issue.
Question: The same questioner asked if performance-based standards would be the way to
advance an alternative technique.
Answer: Mr. Telliard replied that it would. He qualified this by saying that it appears that
performance-based methods will require meeting detection limits and method
specifications, and as the present oil and grease method has no specifications,
there is nothing to which to compare a new method. He indicated that after a
new solvent is chosen, a method detection limit study and a round robin study
would be performed to establish method specifications. Also, solvent
comparability to Freon 113 will be studied to avoid "accidental noncompliance"
with permit requirements due to the use of the new solvent.
Question: A member of the audience stated that the oil and grease method is why they are
14
-------
Answer:
Question:
Answer:
Question:
Answer:
Question:
Answer:
Question:
Answer:
Question:
Answer:
Question:
in "accidental noncompliance."
Mr. Telliard corrected himself and said there is no such thing as
noncompliance."
"accidental
A member of the audience asked how a solvent substitution would work in terms
of permit limits and compliance.
Mr. Telliard explained that if the substitute (not equivalent) solvent produced
results greater than Freon 113 does, there would be a permit compliance issue.
If the substitute solvent always gives results lower than Freon 113, then EPA
could change the solvent via the Federal Register notice and comment process,
and all permit numbers would stay the same. At the time of permit renewal, the
new solvent could be factored in, based on the data the permittee had been
collecting using the new solvent. Another option would be to have every
permittee develop a correction factor based on measurements of the same samples
with Freon 113 and the new solvent and use the correction factor to amend the
permit. He allowed that implementing the solvent change in terms of permits
would be difficult, and that EPA was going to have to find the most cost-effective
way to do it.
A member of the audience asked if research on alternative methods would
continue beyond the December deadline for choosing the substitute solvent.
Mr. Telliard replied that he hoped to eventually do away with the oil and grease
measurement, and allow it to be replaced by another technique or techniques. He
cautioned that further research was resource-dependent, and that the priority of
actions was to find a substitute solvent, determine whether a correction factor is
needed, and then look at how to phase out the oil and grease test. He added that,
at the same time, it was necessary to avoid any "technical" noncompliances.
A member of the audience asked what the purpose of the oil and grease test was.
Mr. Telliard replied that it was a continuation of sanitary engineering practice
related to primary Publicly Owned Treatment Works (POTWs).
A member of the audience asked why a "calibrated eyeball" test could not be
used for sheen detection.
Mr. Telliard answered that he had made the suggestion to regulate by using a
sheen number, and requiring further testing if that number is exceeded. He also
mentioned that immunoassay test kits could be used to do screening, and EPA
was looking into that.
A member of the audience asked whether there would be a time period in which
a method to replace oil and grease would be integrated into the standard methods.
Mr. Telliard replied in the affirmative.
The same questioner asked if implementation of a new method would have to be
15
.
-------
Answer:
Question:
Answer:
Question:
Answer:
contingent upon review of categorical standards and local regulations involving
different industries. If so, would the new method not simply be substituted for
oil and grease.
Mr. Telliard answered that it would not.
The same questioner asked whether regulations would have to be changed because
of a different measurement method.
Mr. Telliard answered that they would.
The questioner expressed concern about how this would be interpreted in the
regulated community.
Mr. Telliard replied that that was why this meeting was being held in Boston,
namely, to allow the industries in Region I that had been sampled to express their
views.
Mr. Telliard closed the workshop by thanking the attendees for coming, and asked
them to provide him with any other comments or information they might have to share before
the anticipated time of the decision on the oil and grease method.
16
-------
Appendix A
Workshop Agenda
-------
-------
OIL AND GREASE WORKSHOP
WEDNESDAY JUNE 30, 1993
Agenda
Chairman: William A. Telliard
1:00 -1:15 Welcome and Introduction
1:15 - 1:45 Freon Replacement Study, Phase I Study Results
William A, Telliard, U.S. EPA Office of Science and Technology
1:45 - 2:00 Data Evaluation and Statistics, Phase I Study Results
Roger Litow, DynCorp Viar, Inc.
Solid-Phase Extraction
2:00 - 2:15 EPA Region III Analysis Using Solid Phase Extraction Columns
William A. Telliard, U.S. EPA Office of Science and Technology
2:15 - 2:30 Evaluation of Solid Phase Extraction Columns for Analysis of Oil and
Grease in Aqueous Samples
Rex Hawley, Varian Sample Preparation Products
2:30 - 2:45 Oil and Grease Analysis in Wastewater Using Solid Phase Extraction Disks
Craig Markell, The 3M Corporation
2:45-3:00 Break
Infra-Red
3:00 - 3:15 Oil and Grease Samples using NDIR and Flon S-316
William Eckel, DynCorp Viar, Inc.
3:15 - 3:30 Determination of Oil and Grease by Evaporation of Solvent in a Quartz
Cell in an Infra-red Spectrophotometer
Jerry DiMenna, Buck Scientific
3:30-4:15 Open Discussion
4:15-4:30 Closing Remarks
-------
-------
Appendix B
Presentation Materials
"Freon Replacement Study, Phase I Study Design*
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Presentation Materials
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Presentation Materials
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Appendix £
Presentation Materials
"Oil and Grease Analysis in Wastewater Using
Solid Phase Extraction Disks"
Craig Markell, The 3M Corporation
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-------
Appendix F
Presentation Materials
"Evaluation of Oil and Grease Samples Using NDIR
and Flon S-316"
William Eckel, DynCorp Viar, Inc.
-------
-------
-------
Preliminary Report of EPA Efforts to Replace Freon for the Determination of Oil and Grease
. - -
Exhibit 10.
Summary Statistics For Alternative Techniques in the Determination of Oil and Grease
Aqueous Waste Stream, Infrared Analysis
All Samples (N»36)
Solvent
Sep. Funnel Freon
Ron
Mean
1.00
1.62
SD
—
1.55
RSD
—
96
Median
1.00
1.01
RMSD
1.5'
8.3
Non-Petroleum
-------
Preliminary Report of EPA Efforts to Replace Freon for the Determination of Oil and Grease
Exhibit 14.
Normalized Root Mean Square Deviations
Aqueous Waste Stream, Alternative Techniques
Non-Petroleum Samples
'£.
a
*
a
Q
V)
15 -i
12-
9-
6-
3 -
v SPE 47 mm Disk
v SPE 90 mm Disk
G SPE Column (new)
• infrared
Acceptance Limit
J7 SPE Column
[[[ SPE Disk
...T...T. .-,.•,. .T.T.T_T.T.T.......T.T.T.T.T...*.....W...T.......T.....1.....*.T.<. fafa^Q
Hexane MeCl2 Perchlor 80/20 Freon MTBE Ron
Solvent
NOTE: Points below the respective Acceptance Limit'ire not significantly different from separatory funnel extraction with Freon
June 1993
-------
Preliminary Report of EPA Efforts to Replace Freon for the Determination of Oil and Grease
Exhibit 15.
Normalized Root Mean Square Deviations
Aqueous Waste Stream, Alternative Techniques
Petroleum Samples
10 n
8-
6 -
CA
4 -
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Hcxanc MeCl2 Perchlor 80/20
Solvent
Freon
MTBE
v SPE 47 mm Disk
T SPE 90 mm Disk
n SPE Column (new)
• Infrared
Acceptance Limit
SPE Column
--.. SPE Disk
Infrared
Ron
36
June 1993
-------
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-------
Appendix G
Presentation Materials
"Determination of Oil and Grease by Evaporation of Solvent
in a Quartz Cell in an Infra-red Spectrophotometer"
Gerald DeMenna, Chem-Chek Laboratories
-------
-------
12:25 ID:BUCK SCIENTIFIC TEL NO:20385305G9 8136 P01
Scientific
BUCK Scientific, Inc.
58 Port Point Street • East Norwalk, Connecticut 06855 • (203) 853—9444
Ms. Lynn Riddick
EPA
Material from Oil & Grease lecture in Norfolk, VA
ENVIRONMENTAL OIL £ GREASE
ANALYBIBt An Overview
A NOVEL Technique for using LESS Freon
and non-"Freonlt solvents
[Using existing XR Photometers]
Gerald J. DeMenna, Chem-Chek Consulting
44 Stelton Road, Piscataway, NJ 08854
[908] 752-7793
16th. Annual EPA Meeting // 4 May 1993
Norfolk, Virginia
CURRENT METHODOLOGIESI
[l] Extraction and Gravimetric Isolation
of TPH materials
[2] Extraction and Liquid Cell IR Filter
Photometry of TPH (OH) Absorptions
[3] Gas Chromatographic Separation
with.FID Detection for TPH
PROPOSED PROCEDURES
For use with existing Infra-Red filter Photometers
optimized for the 3.4 micron / 2950 cm-1 absorption
bands found in ALL hydrocarbon materials
without using large volumes of FREON or
using non-FREON type solvents (Methylene Chloride)
FAX No. 203-853-0569 TELEX No. 643589 BUCK Sd ENLX
-------
J3ay-20-l93 12:26 IDsBUCK SCIEKTIFIC
TEL NO:2038530569
8136 P02
PROPOSED PROCEDURE:
[1] Prepare the sample and perform the
extraction per standard protocols
(SW-846 / #9070-9071)
[2] Downscale the Volume or weight of
FREOK used for the extraction by
a factor of 2 to 10
[dependant on sample matrix]
[)] "Cast" a film of TPH material from
the FREON on a XR-Quartz "cavity" cell
IN8TRUXEKTATION1
Model HC-404 Total Petroleum Hydrocarbon
analyser
[Filter IR Photometer w/ 20 cm-l bandpass
at 3.42 microns]
Normal Analyses w/ 10mm. iR-Quartz
Liquid Cell using Freon-113
Purchased from BUCK Scientific, Inc.,
E. Horwalk, CT
PRINCIPLESI
Like the existing gravimetric
procedure, the "evaporation method"
will allow the Freon solvent to volatilize
and leave the TPH materials as a film
residue in a XR-transparent Quartz plate.
Standards and spikes carried through the
procedure are used for calibration
and recovery calculations.
-------
Appendix H
Presentation Materials
"Phase I Study Conclusions and
Strategy Options for Regulation Oil and Grease"
William A. Telliard, U.S. EPA Office of Water
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-------
-------
mV-2a~'93 12:26 ID:BUCK SCIENTIFIC TEL N0:2038530569 8136 P03
BENEFITS of NEW PROCEDUREI
[1] Allows use of significantly lower
volumes of regulated solvents.
[2] Allows use of other suitable
solvents with similar partitioning
coefficients
[methylene chloride for this study]
Evaluation of Method Correlations
Test three (3) varied types of
samples for TPH by:
[l] Gravimetric Technique
[2] IR Photometer w/lOmm. Liquid Cell
[3] IR Photometer w/ "cavity cell"
« NOTE - All extractions done with
Freon-113
sample #u polymer Fabrication Plant,
Elisabeth* NJ / discharge line
Data from triplicate preps w/ statistics,
with 5 PPM spike for recovery study
[1] GRAY [2] IR-LIQ [3] IR-EVAP
25 PPM 31 PPM 28 PPM
(5.5% RSD) (3.7% RSD) (4.2% RSD)
31 PPM 36 PPM 33 PPM
(spike recovery 99+% overall]
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mY-20-'93 12:27 ID:BUCK SCIEKTIFIC
TEL NO:2038538569
8136 P04
sample #2: Pharmaautioal Kaufacturer,
Wilmington, DB / pond aludge
Data from triplicate preps v/ statistics,
with 50 PPM spike for recovery study
[1] GRAV
140 PPM
(3.9% RSD)
[2] IR-LIQ
155 PPM
(2.4% RSD)
[3] IR-EVAP
150 PPM
(3.2% RSD)
195 PPK 202 PPM 201 PPM
[spike recovery 97+% overall]
Sample f3i Commercial Development Bite,
If e a tones ter, mr / mixed soil oorings
Data from triplicate preps v/ statistics,
with 10 PPM spike for recovery study
[1] GRAV
52 PPM
(4.1% RSO)
£2] IR-LIQ [3] IR-EVAP
55 PPM
(3.4% RSD)
53 PPM
(3.0% RSD)
61 PPM 65 PPM 64 PPM
[spike recovery 98+% overall]
PRELIMINARY COMPARATIVE STUDY*
Preon-113 vs. Methylene Chloride
on the "cavity cell"
Sample: Machinery Shop effluent
Freon-113 CH2C12
87 PPM
(3.3% RSD)
91 PPM
(3.5% RSD)
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MPY-20-*93 12:27 ID:BUCK SCIENTIFIC
TEL NO:2038530569
P05
Performance specification*
[based on 250uL aliquot in Sum x 4mm
cavity in IR-Quartz plate]
Sensitivity:
Detection Limit:
1.5 PPM gives 0.004A signal
4 PPM gives 10% reproducibillty
at approx. 0.01A
Linearityt Correlation of 0.98 up to 250 PPM
CONCLUSIONS*
This technique is adaptable to all
IK Photometric units with an open sample
compartment to allow use of the "cavity cell"
evaporation plate.
Additional studies with other solvents
and a variety of sample matrices
is required to fully develop the
potential usefulIness of the method.
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