A lot of plastics in our homes are not just made of
polymer. Many have monomeric additives
within them and sometimes these additives represent a significant portion of
the mass of the plastic. For example,
the plasticizer in flexible PVC is
typically greater than 10% and can be has high as 30-40%. Phthalates are often used as the
plasticizer to make PVC flexible. All phthalates are
monomers and all will diffuse out of the plasticized PVC matrix given enough
time to do so. The typical mechanism for plasticized items
used indoors is for the plasticizer to diffuse out of the PVC and then
partition into house dust. Must of house
dust is composed of our shredded skins cells and are therefore expected to be lipophilic. The plasticizer would partition into the dust and
the dust would be distributed within the residence. Of course, some will be cleaned and removed
but it is difficult to determine how much might be removed before human
exposure may occur. What we do know it that there is a significant amount of phthalates in the dust of some homes. The dominant source
of exposure is anticipated to be hand to mouth ingestion of this dust with kids
doing more than adults but adult doing at least some of this type of ingestion
our entire lives.
While researching this issue on the Internet I found the
following data for a PVC “geomembrane” which is another way of saying a canal
liner that was used to contain water. They
report that the PVC films was 30-35% plasticizer but I did not find out which
plasticizer they used. Their report
shows the following loss of plasticizer to the water.
Service
Years
2
4
5
9
14
19
Original
Specification
Value
|
Plasticizer
Content
Remaining
92.1%
67.7%
67.8%
65.6%
58.0%
54.3%
None
|
I am frankly not
sure how this relates to plasticizer diffusing from a PVC product to its
surface to be then transported within the indoor environment via dust; however,
it is an interesting study.
It should be mentioned that plasticizers are the not only
monomers to diffuse out of plastic.
Indeed, any monomer would be expected to do so including flame
retardants. Indeed, some flame
retardants appear in the plastics of our electronic cases at concentrations
around 10% and are thus prime candidate for the migration-to-dust-to-ingestion pathway.
It turns out there has been a tool around for some time
that was developed in 1989 by Arthur D. Little, Inc for the EPA Office of Pollution Prevention and
Toxics, Economics, Exposure, and Technology Division, Exposure Assessment
Branch (EAB). It is an “oldie but
goodie”. Indeed, it is a DOS
program that EPA claims can be run in the modern Windows (7 or 8? ) environment. I keep an old PC around just to run this
old stuff (it runs DOS 6.2, Windows 3.2 and Windows XP) so I am not sure if AMEM will run on Windows 7 or 8. If anyone
has any experience with this, please let me know.
You can download and learn about it at: http://www.epa.gov/oppt/exposure/pubs/amem.htm A cut and paste of some of the Q&A from
this EPA site is presented below:
The model assumes:
·
The chemical is
homogeneously distributed throughout the polymer and is not initially present
in the phase external to the polymer,
·
Migration of the
chemical is not affected by the migration of any other chemical or by the
penetration into the polymer of any component of the external phase,
·
The migration is
isothermal,
·
and Fick's law of
diffusion and convective mass transfer theory applies.
How Does AMEM Work?
AMEM is a DOS-based software product developed
in 1989 that uses a family of mathematical equations that address simple and
complex scenarios for chemical migration through a specific polymer. The more
complex equations require more input data. Using the model, you may:
·
Develop migration
estimates,
·
Consider the effect of
chemical partitioning between the polymer and the external phase,and
·
Consider the effect of
mass transfer resistances in the external phase.
In all cases the model estimates the fraction
migrated (i.e., the fraction of the chemical initially present in the polymer
that migrates) after a specified duration. This model only provides one
parameter needed to estimate exposure. The user must then use other equations
and/or models to estimate exposure.
What Do I Need to Use AMEM?
Polymer category (i.e., Silicone Rubber, Natural
Rubber, LDPE, HDPE, Polystyrene, or unplasiticized PVC) or diffusion
coefficient of the polymer. (MAJ Note: This is the first I have noticed the category of unplasticized PVC. I think, however, the program and documentation might still present some insight for the estimation of phthalate out of PVC).
·
Molecular weight of
additive.
·
Total polymer sheet
thickness (cm) External phase (i.e., air, water, or solid)
·
One or two sided
migration Time frame of interest
What Type of Computer System Do I Need?
·
Processor -
IBM-compatible computer with a Pentium microprocessor (minimum speed: 33 MHZ)
·
Memory - 640K
·
Hard disk space - 2 MB
·
Operating System - AMEM
is a DOS-based program, however, in can be run in a Windows environment by
using key strokes not a mouse.
(Jayjock Note:
640k of memory and 2 MB of hard disk space really shows how far we have
come since 1989).
If anyone knows of a better tool to answer these
questions, please drop me a line and I may write about it here.
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ReplyDeleteDear Dr. Jayjock:
ReplyDeleteI found the EPA i-SVOC (2014) model could do similar estimates of SVOC (e.g. flame retardant) emitting from products (substrate). http://www.epa.gov/nrmrl/appcd/mmd/i-sovc.html
Similarly, it depends the user inputs on a few factors (D: diffusion coefficient of SVOC in the subtrate, Kma: partition coefficient of SVOC between solid and air, ha: mass transfer coefficient in the air and C0: the initial SVOC concentration in the substrate.) The companion model PARAMS 1.0 from EPA can estimate quite a few parameters.
I found the difficult part is to estimate D since we do not have a lot of testing data on SVOC/substrate pair. Liu and et al. published a testing method for estimating D and Kma on Atmospheric Environment 89 (2014) 76-84 which is helpful. I look forward to more data being generated.