Printech Archive, February, 2000
Re: VOC content/photochemical reactivity


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From: DAVE SALMAN (SALMAN.DAVE@EPAMAIL.EPA.GOV)
Date: Fri Feb 25 2000 - 14:51:29 CST


Gary -

One small clarification to the Rule 66 part of your note is that the
non-photochemically reactive compounds that we talk about today
(i.e., those organic compounds which EPA has deemed to have
negligible photochemical rectivity and therefore are not VOCs) are
very different from the Rule 66 "substitution" concept of
photochemically reactive and non-photochemically reactive.

In Rule 66 the definition of Photochemically Reactive Solvent was (I
am taking this from the original Rule 66 adopted on July 28, 1966.
The same definition appears in a January 7, 1977 version of
SCAQMD rules which include definitions in Rule 102 and usage of
solvents in Rule 442):

Photochemically Reactive Solvent means any solvent with an
aggregate of more than 20 percent of its total volume composed of
the chemical compounds classified below or which exceeds any of
the following individual percentage composition limitations, referred
to the total volume of solvent:

(a) A combination of hydrocarbons, alcohols, aldehydes, ethers,
esters or ketones having an olefinic or cycloolefinic type of
unsaturation except perchloroethylene: 3 percent;

(b) A combination of aromatic compounds with eight or more
carbon atoms to the molecule except ethylbenzene, methyl
benzoate and phenyl acetate: 8 percent;

(c) A combination of ethylbenzene, ketones having branched
hydrocarbon strucutres, trichloroethylene or toluene: 20 percent.

The earliest appearance of the current reactive/negligibly reactive
approach that I know of is in a February 5, 1976, Federal Register
notice which announced the availability of a January 29, 1976,
Policy Statement on Use of the Concept of Photochemical Reactivity
of Organic Compounds in State Implementation Plans for Oxidant
Controls.

Does anyone know exactly where they were and what they were
doing on July 28, 1966 - the day Rule 66 was adopted?

>>> <GaryJGATF
@aol.com> 02/25/00 02:34pm >>>
Brian:

I agree with your opinion that VOCs and VOC content determination
is one of
the more simpler, but confusing aspects of environmental
regulation. The more
you look into it, the more complicated it becomes. As Dave Salman
point out
in his response to your email, unless a chemical is placed on the list
of
exempt compounds, it is considered a VOC. In order to get on the
list of
exempt compounds, a formal petition needs to be prepared and
submitted to
EPA. The petition needs to include the scientific data supporting the
claim
for negligible photochemical reactivity.

In terms of determining VOC content, Method 24 is principal
method for many
materials, principally inks and coatings. Method 24 allows for the
subtraction of water and exempt compounds from the final VOC
content
determination.

While the above seems straight forward, the confusion begins in the

determination of the photochemical reactivity of any given chemical.
EPA has
not published a formal protocol on this extremely essential subject.
What
appears to be current policy is that the reactivity of the chemical in
question needs to be compared to that of ethane. Those chemicals
whose
reactivity is greater than ethane are VOCs and those, whose
reactivity is
less, can be placed on the exempt list.

Specifically, the reactivity is measured by how much ozone is
produced on
either a molar or gram basis. The gram basis looks at the weight of
ozone
produced per weight of test compound compared. The other
measure is molar,
which is best thought as a concentration and not weight. EPA has
changed its
position several times over the years on the on significance of the
mole vs.
gram basis and it appears to be shifting back to the mole basis.

As background, acetone was added to the list of exempt
compounds based on the
gram approach to measuring reactivity. When EPA delisted acetone
and those
who follow this issue realized the significance of the shift in policy
from a
molar to a weight basis, EPA was flooded with petitions, including
the
petition submitted by the printing industry to delist ink oil. After the
acetone decision, EPA began to examine its revised policy and has
decided
that a weight basis is far more difficult to defend and is not
technically
accurate.

In discussions with EPA on how photochemical reactivity is defined,
acetone
should be viewed as an anomaly. While it seems to be certain that
ethane will
be used as the benchmark for comparison, the measure of reactivity
has gone
through some changes. Since the vast majority of chemical
reactions are
examined on a molar basis, mole comparisons are more
scientifically
acceptable. It is interesting to note that on a molar basis acetone
produces
more ozone than ethane.

Therefore, in the methyl acetate decision, EPA stated that only
those
compounds that produce less ozone than ethane on a molar basis
would be
considered for delisting. The good aspect for methyl acetate is that
is less
reactive than ethane on both a molar and gram basis. EPA's
position in the
proposal to delist t-butyl acetate also further strengthens the molar
approach. However, EPA did solicit comment on how reactivity
should be best
defined.

The standard approach to measuring photochemical reactivity is to
use a smog
chamber, which simulates what would happen to the test
compound as it is
released into the air. There are two active smog chambers in the
US, one in
California and the other in North Carolina. Each smog chamber
uses a
different approach to generate data. One uses a simpler urban air
mix as the
matrix and UV lights, while the other uses a more complex urban air
mix and
sunlight to drive the photochemical reactions. EPA generally likes to
see
data from both chambers in evaluating the reactivity of a chemical.

Computer models complimented with actual research data have not
evolved to a
point where a structure activity relationship can be easily predicted.
There
is some research being conducted in this area, but it is not sufficient
to
have definitive conclusion for the very near future. Some of the
research has
also indicated that the reactivity of any given compound is greatly
influenced by the "environment" in which it is emitted. Several
studies have
shown that the reactivity of ethane, which was once thought of
being stable,
actually varies.

It is also interesting to note that some of the older literature on
photochemical reactivity indicates that hexane along with other
chemicals is
not photochemically reactive. This conclusion was based on some
early work
performed in the 1960's and 1970's. The concept of just regulating
photochemically reactive chemicals was first incorporated into
regulation via
Rule 66, which was implemented in Los Angles. Other states
quickly followed
suit and you still have today regulations on the books in certain
states that
limit the emissions of photochemically reactive chemicals as well as
VOCs.
These regulations, of course, add confusion to the entire topic of
regulating
air pollution emissions.

The last point to be made in this overall discussion is the role of
Method
24. Method 24 has served as the backbone of VOC content
determination since
the early 1980's. However, it does have some limitations and has
been
modified since its original release. The modifications have not kept
pace
with evolutions in materials. More reactive cured (e.g., UV and EB)
and
water-based materials are used today than in the 1980's and this
has placed
demands on Method 24. While Method 24 has been modified, it
needs to be
further modified. One good modification that occurred was to
address VOC
content determination of reactive cured materials. The problem is
that the
modification only accommodates "thick film" inks, paints, and
coatings. The
method still can't be used for thin film materials, such as UV inks
and
coatings used by printers. An ASTM subcommittee is currently
working on a
modification, but until one is designed, approved, and adopted, it
could be
years. In the interim EPA is working on some guidance.

The other major problem with Method 24 is that it can't tolerate
materials
with high levels of water. While there are some precision
adjustments
permitted, its precisions and reproducibility with water-based
materials
leaves a lot to be desired. EPA has been working on this problem
for several
years, but has yet to find an appropriate solution. EPA does have
some
existing guidance on precision adjustments.

To a lesser extend, there have been problems reported with
precision and
reproducibility with solvent-based materials, which were the
materials that
the method was designed to measure. It seems that if the same
sample is sent
to different labs, you can get different results. I only have a limited
amount of data on this topic and a thorough evaluation of this
problem with
graphic arts materials needs to be performed.

I hope that the above answer has shed some light on your question.
If you
have any more questions, let me know.

Gary Jones
Graphic Arts Technical Foundation
200 Deer Run Road
Sewickley, PA 15143
412/741-6860 x608 - Phone
412/741-2311 - Fax
Dave Salman
Coatings and Consumer Products Group
US EPA OAQPS (Mail Drop 13)
RTP NC 27711
tel (919) 541-0859
fax (919) 541-5689
e-mail salman.dave@epa.gov


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