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Executive Summary of Photolysis Studies
3M has completed a series of studies of the direct and indirect photolytic reactions of four materials; Table 1 lists the materials, their chemical abbreviations, and the relevant 3M report numbers. The purpose of the studies was to provide information regarding the photolytic stability of these materials under environmentally relevant conditions. The materials were specific (monomeric) compounds potentially related to the manufacture and/or environmental persistence of the more complex materials.
Three of these studies are based on samples in aqueous solutions. The analytical methods developed by 3M for these studies are e Ts -9-46.0, ETS-9-44.0, ETS-9-49.0, ETS-8-177.0, ETS-8-176.0, ETS-8-182.0, and ETS-8-181.0. The methods are based on OPPTS: 835.5270 and the OECD Draft Document "Phototransformation of Chemicals in W ater - Direct and Indirect Photolysis" (August 2000). The studies are GLP-like; many GLP standards were used in the studies, and the quality assurance procedures followed were based on the practices described in the GLP documentation (40 CFR Part 792, TSCA).
The three aqueous studies included the preparation of replicate samples of each material at 25C under several radical precursor conditions. After incubation under UV irradiation and over specific time periods, samples were analyzed by HPLC/MS and/or GC/MS to provide quantitative information on the test compounds and potential degradation products.
First-order kinetic theory provides a suitable framework for interpretation of all the analytical results; Table 2 lists the results of these interpretations.
No evidence of direct photolysis was noted in any of the studies.
In the indirect photolysis studies of PFOS and PFOA, no degradation products were observed. However, using data obtained for the iron-rich matrix (with and without added H2O2), an estimated minimum indirect photolytic half-life was calculated.
Indirect photolytic degradation of W-EtFOSE alcohol was observed in each test matrix, but the observed rates and product distribution varied from matrix to matrix. The three primary degradation products observed were PFOA, W-EtFOSA, and FOSA; however, under certain conditions, trace levels (near the quantitation limits) of other potential degradation products (heptadecafluorooctanes and PFOS) were also observed. It remains unclear whether these compounds were produced by the degradation of W-EtFOSE alcohol or by degradation of low-level impurities in the original test material.
One study (that of POSF) employed gas phase samples prepared at 33C. In these studies, an ultraviolet lamp irradiated various sample and control mixtures of POSF, CH3Cl (a reference compound), ozone and water vapor in a reaction chamber. FTIR spectroscopy provided in-situ measurements of the reactant concentrations under various sample and control conditions. The POSF study showed degradation in only one of seven runs. Data
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from that run, in conjunction with published values of the tropospheric OH radical concentration and related reaction rates for CH3Cl, provides an estimate of the minimum POSF half-life due to reactions between POSF and the OH radical.
T able 1. In form ation R egard in g C om pounds In volved in In d irect P h otolysis Studies
Compound
A b b rev ia tio n
3M Report Number and Date
Perfluorooctanesulfonate - potassium salt
PFOS
W 2775 (April 23, 2001)
2-(A -E thylperflu oroctan esu lfonam id o)-ethyl alcoh ol
A -EtFOSE alcohol
W 2783 (April 19, 2001)
Perfluorooctanoic acid - am m onium salt
PFOA
E 00-2192 (April 20, 2001)
Perfluorooctanesulfonyl fluoride
POSF
E 01-0739 (June 12, 2001)
Table 2. Sum mary of Indirect Photolysis Study Results
Max.
Photolysis
M atrices
Period
Com pound Abbreviation
Studied
(hours)
Aqueous:
PFOS
H 2O (pH 7) Iron o x id e/H 2O 2
167
Synthetic Humic
Aqueous:
H 2O (pH 7)
A -EtFOSE alcohol
Iron o x id e/H 2O 2
72
Synthetic Humic
H 2O 2 -rich
Aqueous:
PFOA
H 2O (pH 7) Iron o x id e/H 2O 2
164
Synthetic Humic
Gaseous:
POSF
O 3, H 2O , CH3C l in the presence o f U V
N /A
radiation
E stim ated Half-Life at
25C > 3.7 years*
40 days
> 349 days*
> 3.7 years*
No loss of parent analyte quantified. The > result is based on measurement uncertainties.